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Introduction
Background: What is the Zeta
Potential?
The ZetaProbe and AcoustoSizer II have
Colloidal particles are usually
become routine instruments for the
electrically charged. They are
measurement of particle size and zeta
surrounded, in suspension by a
potential in colloidal systems. One of the
cloud of ions that carry an equal and
great advantages of these devices is that
opposite charge. The zeta potential
they can measure size and zeta without
is the voltage difference between
dilution.
the particle surface and the liquid
beyond the charge cloud. In colloids
The traditional devices for measuring
that are electrostatically stabilized,
size and zeta use optical techniques such
zeta provides a measure of the
as light scattering. The samples need to
electrical repulsive force between
be quite transparent to use these
the particles. For other systems
products, and this usually means they
where the stability comes from
must be diluted down to concentrations
steric components, the zeta
of approximately 10 mg per litre. Even
potential can be used as a measure
the more recent optical devices that
of the state of the surface. It can be
claim to be able to measure zeta
used to monitor optimum levels of
potential in ‘concentrated’ suspensions
dispersant or other agents to be
can only do so at concentrations of 0.5
added to the particles.
% w/v under favourable conditions of
low opacity. This is still one to two
Thus zeta potential can be used for
orders of magnitude more dilute than
monitoring and controlling colloid
most colloids.
stability and as an indicator of the
This dilution is time consuming, an particle surface chemistry.
important consideration in QC labs
where sample throughput is vital. And
the dilution can lead to large errors in light, and so it is not necessary to see
the zeta potential if there is a change in through the suspension to measure it.
the concentration of the background
electrolyte. Furthermore, the diluted Two measurement techniques are
sample has such a small particle surface employed – electroacoustics and
area that the zeta can be altered by ultrasonic attenuation. The first
trace amounts of surface-active technique is used in both products, while
impurities in the sample. the attenuation method is only used in
the AcoustoSizer II, for getting particle
How can the ZetaProbe and AcoustoSizer size.
II measure in concentrates? The reason
is that they measure sound rather than
We will begin our description with the up by a piezoelectric transducer shown
electroacoustic method, since this is on the left-hand side of the diagram.
common to both products.
The ESA depends on the particle
THE ESA MEASUREMENT velocity, which in turn depends on the
particle charge. The ESA also depends
on the particle size, for bigger particles
In this technique we measure ultrasound
generated by the particles. A MHz have more inertia, and this causes them
voltage is applied across a pair of to lag behind the electric field. Thus
there will be a time delay between the
electrodes in contact with the
field changing direction and the particle
suspension. Colloidal particles are
velocity changing direction. Hence the
electrically charged, so they move back
and forth, first towards one electrode particle size affects the phase of the
and then the other. It is this particle ESA, and so by measuring the
magnitude and phase of the ESA sound
motion that generates the ultrasound, in
wave we can determine both particle
the same way that the back and forth
charge (or zeta potential) and size.
motion of a loudspeaker generates
sound. The sound wave from each
particle is very tiny, but the particles The dynamic mobility
move in phase and this cooperative
motion results in a measurable beam of The ESA depends on particle size and
ultrasound. zeta, but it also depends on the
geometry of the measuring cell, the
This effect, of sound waves generated by strength of the applied field, the material
an applied electric field, is called the the cell is made of, the type of
Electrokinetic Sonic Amplitude Effect, or transducer used and so on. The first step
ESA for short. in the process of getting size and zeta is
to extract, from the measurement, a
quantity that only depends on the colloid
and not on the device used for making
the measurement.
E cos ω t (1)
Figure 1 The AcoustoSizer II ESA measurement
cell will cause the colloidal particles to move
with a sinusoidal velocity
In figure 1 we show a schematic
diagram of the AcoustoSizer V cos (ω t − θ ) (2)
measurement cell. The colloid flows up
between a pair of parallel plate where t is time and ω is the angular
electrodes that are connected to a MHz frequency. The phase angle θ has been
voltage source. The ESA sound wave
introduced to allow for the phase lag
passes out of the suspension and travels
caused by particle inertia.
through a glass block where it is picked
Readers who are not familiar with the Getting the dynamic mobility
terms Mag and Arg may recall that a from the ESA
complex number z can be represented as
a point on the x-y plane, where the x To find the mathematical relation
coordinate is the real part and the y between the measured ESA and the
coordinate is the imaginary part of the dynamic mobility, it is necessary to solve
complex number. The magnitude (or the equations of motion for a colloid
Mag) of z is the distance from the origin subjected to an applied electric field.
to the point (x,y), and the argument The mathematical details are set out in
(Arg) is the angle that the line from the the Appendix of the 2003 paper by
origin to the point makes with the x axis. O’Brien, Jones and Rowlands (see the
Thus the magnitude of the dynamic references for details), where it is shown
mobility is defined in the same way as that
the electrophoretic mobility, and its
argument is minus the phase lag. zs zg ρp − ρ
ESA = A(ω ) φ µD (4)
zs + z g ρ
At low frequencies, the inertia forces are
very small and the particles will move in
phase with the electric field. In this limit There are a number of new terms in this
the dynamic mobility is the same as the formula. The quantity φ is the particle
electrophoretic mobility. But as the volume fraction, that is, the fraction of
From these measurements it can be Thus, in the AcoustoSizer II, the ESA
seen that the mobility magnitudes drop method can be used for getting particle
off more rapidly with frequency for size in the range of about 70 nm to 10
larger particles, and the phase lags microns diameter. For smaller particles
increase more rapidly as the particle size the ESA technique can give the zeta
goes up. Thus the size can be potential, but not the particle size.
determined from the shape of the
dynamic mobility spectrum. And once Our ZetaProbe zeta potential analyzer
the size has been calculated the zeta can also measures the Dynamic Mobility
be determined from the absolute Spectrum but uses a different frequency
mobility magnitudes. range than the AcoustoSizer II. The
ZetaProbe measures the Dynamic
6 -5
Mobility Arg. [degrees]
-10
5
-15
4
-20
8]
3 -25
2 -30
-35
1
-40
0 -45
0.0 5.0 10.0 15.0 20.0 0.0 5.0 10.0 15.0 20.0
Frequency [MHz]
Frequency [MHz]
Nissan 0.3 Micron Cabot SCE Nissan 0.3 Micron Geltech 1.0 Micron
Geltech 1.0 Micron Klebesol 30N50 Cabot SCE Klebesol 30N50
zs zg
S = B (ω ) exp ( −α L ) (7)
( zs + zg )
2
0.5 0.12
0.45
Mean Attenuation Coefficient
0.1
Mean Differential Fraction
0.4
0.35 0.08
0.3
0.25 0.06
0.2
0.04
0.15
0.1 0.02
0.05
0
0
0.001 0.010 0.100 1.000 10.000
0.0 5.0 10.0 15.0 20.0
Diameter [µm] (Logarithmic scale)
Frequency [MHz]
Nissan 0.3 Micron Cabot SCE Nissan 0.3 Micron Geltech 1.0 Micron
Figure 5 The measured attenuation coefficient spectra, and the size distributions obtained from
those spectra for the four silica suspensions of table 1.
The trends in these graphs are not as These sizes for these suspensions are
clear as those in the dynamic mobility consistent with those from those
graphs of figure 3. For the very small obtained from electron micrographs.
Klebesol and Cabot particles, the
attenuation coefficient is small and rises Measurements on
monotonically with frequency. For the concentrated colloids
0.3 micron Nissan suspension the
attenuation is still increasing
A number of independent studies have
monotonically with frequency, but it been undertaken to determine the
seems to be reaching a maximum at the accuracy of our ESA and attenuation size
highest frequency, and for the 1 micron
and zeta estimates in concentrated
Geltech silica is reaches a maximum and
colloids. To carry out these tests it is
then decreases with increasing
necessary to compare the concentrated
frequency. measurements with measurements on
dilute samples. Since dilution can easily
The problem of determining the
alter zeta, and sometimes alter size, the
theoretical link between the attenuation
authors in these studies took great care
coefficient and the particle size is very
to dilute the colloid using the same
similar to the dynamic mobility problem, background electrolyte as that in the
and the same methods can be used to
concentrated suspensions. For
obtain the theoretical formula.
suspensions where the particles readily
sediment, this involves decanting the
We will not go into the theory here, but supernatant after the particles have
one useful feature of the theory that settled out and using it to dilute a small
deserves mention is that the maximum
sample of the concentrated suspension.
in the attenuation coefficient as a
For smaller particles it is necessary to
function of frequency occurs at
separate out the supernatant by
filtration or centrifugation. Of course,
ω = O (ν a 2 ) (9) this is only necessary for carrying out
where a is the particle radius and ν is the comparisons with dilute measurements.
To make ZetaProbe and AcoustoSizer II
kinematic viscosity of the liquid.
measurements in practice there is no
In figure 6 we show ESA zeta potential From this figure it can be seen that the
measurements obtained by Johson at al ESA yields a consistent size over this
(1998) on a series of alumina slurries. concentration range.
The first measurements were made on a
sample with a particle volume fraction of
30%. This sample was then diluted with
1