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Zeta Potential:

A Complete Course in 5 Minutes

The Interaction of Colloids


behavior of concentrated suspen-
Electrokinetics and sions. On standing, a weak matrix
of flocculant particles is formed.
Colloid Behavior This prevents the closely packed
Zeta potential can help you sediment that would form and
understand and control colloidal cause “caking” problems if the par-
suspensions. Examples include ticles were highly stabilized and
complex biological systems such as remained completely discrete.
blood and functional ones like paint. Surface forces at the interface of
Colloidal suspensions can be as the particle and the liquid are very
Uncharged Particles are free to
thick as paste (like cement) or as collide and aggregate. important because of the micro-
dilute as the turbidity particles in scopic size of the colloids. One of
a lake. Water, milk, wine, clay, repulsive forces between them in
the major surface effects is elec-
dyes, inks, paper and pharmaceu- order to keep each particle discrete
trokinetic. Each colloid carries a
ticals are good examples of useful and prevent them from gathering
“like” electrical charge which pro-
colloidal systems. Water is a com- into larger, faster settling agglom-
duces a force of mutual electro-
mon suspending liquid, although erates. Examples include pharma-
static repulsion between adjacent
non-aqueous liquids are used as ceuticals and pastes. Sometimes
particles. If the charge is high
well. In many cases, the perform- we have the opposite goal and want
enough, the colloids will remain
ance of a suspension can be im- to separate the colloid from the
discrete, disperse and in suspen-
proved by understanding the effect liquid. Removing the repulsive
sion. Reducing or eliminating the
of colloidal behavior on such prop- forces allows them to form large
charge has the opposite effect —
erties as viscosity, settling and flocs that settle fast and filter eas-
the colloids will steadily agglomer-
effective particle size. ily. Viscosity is another property
ate and settle out of suspension or
that can be modified by varying the
We can often tailor the charac- form an interconnected matrix.
balance between repulsion and at-
teristics of a suspension by under- This agglomeration causes the
traction.
standing how individual colloids characteristics of the suspension
interact with one another. At times In some cases, an in-between to change.
we may want to maximize the state of weak aggregation can be
Particle charge can be controlled
the best solution. Paints are a good
by modifying the suspending liq-
example. Here, the weak aggrega-
uid. Modifications include chang-
tion causes viscosity to be a func-
ing the liquid’s pH or changing the
tion of shear rate. Stirring will
ionic species in solution. Another,
produce enough shear to reduce
more direct technique is to use sur-
the viscosity and promote blend-
face active agents which directly
ing.
adsorb to the surface of the colloid
Reversible aggregation is also and change its characteristics.
useful in controlling the settling

Charged Particles repel each other.

Zeta-Meter Inc. 1
The diffuse layer can be visualized as a charged
atmosphere surrounding the colloid.

colloid; this layer of counter-ions is because they are repelled by the


The Double Layer known as the Stern layer. negative colloid. Negative ions are
called co-ions because they have
Additional positive ions are still
The double layer model is used the same charge as the colloid.
attracted by the negative colloid,
to visualize the ionic environment Their concentration will gradually
but now they are repelled by the
in the vicinity of a charged colloid increase with distance, as the re-
Stern layer as well as by other
and explains how electrical repul- pulsive forces of the colloid are
positive ions that are also trying to
sive forces occur. It is easier to screened out by the positive ions,
approach the colloid. This dynamic
understand this model as a se- until equilibrium is again reached.
equilibrium results in the forma-
quence of steps that would take
tion of a diffuse layer of counter- The diffuse layer can be visual-
place around a single negative col-
ions. They have a high concentra- ized as a charged atmosphere sur-
loid if its neutralizing ions were
tion near the surface which gradu- rounding the colloid. The charge
suddenly stripped away.
ally decreases with distance, until density at any distance from the
We first look at the effect of the it reaches equilibrium with the surface is equal to the difference in
colloid on the positive ions (often counter-ion concentration in the concentration of positive and nega-
called counter-ions) in solution. solution. tive ions at that point. Charge
Initially, attraction from the nega- density is greatest near the colloid
In a similar, but opposite, fash-
tive colloid causes some of the posi- and gradually diminishes toward
ion there is a lack of negative ions
tive ions to form a firmly attached zero as the concentration of posi-
in the neighborhood of the surface,
layer around the surface of the tive and negative ions merge to-
gether.
Positive Counter-Ion The attached counter-ions in the
Negative Co-Ion Stern layer and the charged at-
mosphere in the diffuse layer are
what we refer to as the double
layer. The thickness of this layer
depends upon the type and concen-
tration of ions in solution.

Highly Negative
Colloid

Stern Layer

Two Ways to Visualize the Double


Layer
Diffuse Layer
The left view shows the change in
charge density around the colloid. The
right shows the distribution of positive
Ions In Equilibrium and negative ions around the charged
With Solution colloid.

2
The electrokinetic potential between the
surface of the colloid and any point in the
mass of the suspending liquid is referred
to as the surface potential.

Zeta Potential
Surface Potential
The double layer is formed in
order to neutralize the charged col- Stern Layer
Diffuse Layer loid and, in turn, causes an elec-
Ion Concentration

Zeta Potential
trokinetic potential between the
surface of the colloid and any point Diffuse Layer
in the mass of the suspending liq-

Potential
uid. This voltage difference is on
Zeta Potential
the order of millivolts and is re- (Low Concentration)
ferred to as the surface potential.
The magnitude of the surface
potential is related to the surface
Distance From Colloid charge and the thickness of the Distance From Colloid
Variation In double layer. As we leave the sur-
Ion Concentration face, the potential drops off roughly
linearly in the Stern layer and then Zeta Potential vs. Surface Potential
exponentially through the diffuse The relationship between zeta
layer, approaching zero at the potential and surface potential
imaginary boundary of the double depends on the level of ions in the
layer. The potential curve is useful solution.
because it indicates the strength of
Charge Density

considered to be rigidly attached to


Diffuse Layer the electrical force between par- the colloid, while the diffuse layer
ticles and the distance at which is not. As a result, the electrical
this force comes into play. potential at this junction is related
A charged particle will move with to the mobility of the particle and is
a fixed velocity in a voltage field. called the zeta potential.
This phenomenon is called electro- Although zeta potential is an
phoresis. The particle’s mobility is intermediate value, it is sometimes
related to the dielectric constant considered to be more significant
Distance From Colloid and viscosity of the suspending liq-
Charge Density than surface potential as far as
uid and to the electrical potential electrostatic repusion is concerned.
Variation at the boundary between the mov-
ing particle and the liquid. This Zeta potential can be quantified
Variation of Ion Density in the by tracking the colloidal particles
Diffuse Layer
boundary is called the slip plane
and is usually defined as the point through a microscope as they mi-
The figures above are two representa-
tions of the change in charge density where the Stern layer and the dif- grate in a voltage field.
through the diffuse layer. One shows fuse layer meet. The Stern layer is
the variation in positive and negative
ion concentration with distance from a
negative colloid. The second shows
the net effect — the difference in
positive and negative charge density.

Zeta-Meter Inc. 3
The DLVO theory explains the tendency of colloids
to agglomerate or remain discrete.

The height of the barrier indicates


Distance Between Colloids how stable the system is. In order
The Balance of
to agglomerate, two particles on a
Repulsion & Attraction collision course must have suffi-

Attractive Energy
The DLVO Theory (named after cient kinetic energy due to their
Derjaguin, Landau, Verwey and Van der Waals
velocity and mass, to “jump over”
Overbeek) is the classical explana- Attraction this barrier. If the barrier is
tion of the stability of colloids in cleared, then the net interaction is
suspension. It looks at the balance all attractive, and as a result the
between two opposing forces — elec- particles agglomerate. This inner
trostatic repulsion and van der region is after referred to as an
Waals attraction — to explain why energy trap since the colloids can
some colloidal systems agglomer- be considered to be trapped together
ate while others do not. by van der Waals forces.
Van der Waals Attraction is shown as
a negative curve. In many cases we can alter the
Electrostatic repulsion becomes
significant when two colloids ap- environment to either increase or
Van der Waals attraction is ac- decrease the energy barrier, de-
proach each other and their double
tually the result of forces between pending upon our goals. Various
layers begin to interfere. Energy is
individual molecules in each col- methods can be used to achieve
required to overcome this repul-
loid. The effect is additive; that is, this, such as changing the ionic
sion. An electrostatic repulsion
one molecule of the first colloid has
curve is used to indicate the energy
a van der Waals attraction to each
that must be overcome if the par- Electrical
molecule in the second colloid. This Repulsion
ticles are to be forced together. It
is repeated for each molecule in the
has a maximum value when they Net Interaction
first colloid, and the total force is
Repulsive Energy

are almost touching and decreases Energy


the sum of all of these. An attrac-
to zero outside the double layer. Energy
tive energy curve is used to indi-
The maximum energy is related to Barrier
cate the variation in van der Waals
the surface potential and the zeta
force with distance between the
potential.
particles.
The DLVO theory explains the
tendency of colloids to agglomerate Distance Between Colloids
or remain discrete by combining
Attractive Energy
Repulsive Energy

the van der Waals attraction curve


with the electrostatic repulsion Energy Trap
Electrical curve to form the net interaction
Repulsion
energy curve. At each distance,
the smaller value is subtracted from Van der Waals
Attraction
the larger to get the net energy.
The net value is then plotted —
above if repulsive and below if at-
Distance Between Colloids
tractive — and a curve is formed. If
there is a repulsive section, then Interaction
The net interaction curve is formed by
Elecrostatic Repulsion is always the point of maximum repulsive
subtracting the attraction curve from
shown as a positive curve. energy is called the energy barrier. the repulsion curve.

4
In many cases we can alter the environment to
either increase or decrease the energy barrier,
depending upon our goals.

0 Effect of Type and Concentration of


Electrolytes
AlCl 3 3:1 Simple inorganic electrolytes can have
-10 CaCl 2 2:1 a significant impact on zeta potential.
KCl 1:1
K 2 SO4 1:2
The effect depends on the relative
-20 valence of the ions and on their
Na4 P2 O 7 1:4
concentration. Relative valence can
Zeta Potential, mV

also be thought of as the type of


-30
electrolyte, with type being the ratio
between the valences of the cation
-40 and the anion.
In this example, the zeta potential of a
-50 dilute suspension of colloidal silica was
modified by adding different electro-
lytes. Aluminum chloride is a 3:1
-60
electrolyte and its trivalent cations
easily push the zeta potential toward
-70 zero. Contrast this with the effect of
1 10 100 1,000 10,000 100,000 potassium sulfate, a 1:2 electrolyte.
Concentration of Electrolyte, mg/L First the zeta potential becomes
increasingly negative until a plateau is
environment, or pH, or adding Mechanical bridging by poly- reached at about 50 mg/L. At about
surface active materials to directly mers can be an effective floccu- 500 mg/L, the zeta potential begins to
affect the charge of the colloid. In lating technique. Some long chain decrease because the ions are
each case, zeta potential measure- polymers are large enough to ad- compressing the double layer.
ments can indicate the impact of sorb to the surface of several par-
the alteration on overall stability. ticles at the same time, binding
them together in spite of the elec-
Nothing is ever as simple as it
trostatic forces that would normally
first seems. There are other effects
make them repel each other.
that must be considered whenever
you work with particle stability. In practice, a combination of ef-
Steric stabilization is the most sig- fects can be used to create stable
nificant one. Usually this involves systems or to flocculate them. For
the adsorption of polymers on par- instance, stable dispersions can be
ticle surfaces. You can visualize created by a combination of electro-
the adsorbed layer as a barrier static repulsion and steric hin-
around each particle, preventing drance. Electronegative disper-
them from coming close enough for sions can be flocculated using long
van der Waals attraction to cause chain cationic polymers which si-
flocculation. Unlike electrostatic multaneously neutralize charge
stabilization, there are no long and bridge between adjacent par-
range repulsive forces and the par- ticles.
ticles are subject to attractive forces
until the outer portions of the steric
molecules contact each other.

Zeta-Meter Inc. 5
Adhesives Beverages
Agricultural Chemicals Biochemistry
Asbestos Biomedicine
Atomic Energy

Zeta Potential Applications

Minerals & Ores Clays & Drilling Fluids Ceramics


Many raw mineral ores such as Clays are an essential part of Slip casting is used in volume
those for copper, lead, zinc and paper, adhesives, ointments, rub- production of ceramic ware. A sus-
tungsten are separated by first ber and synthetic plastics. In each pension of clay is prepared and
grinding the ore, mixing it with a of these systems, we have to deal poured into porous molds, which
collector and suspending it in wa- with dispersions of clay in water or draw off the water from the clay
ter. The next step is flotation. Air other fluids. Clay colloid chemis- particles by capillary action. A fil-
is bubbled through the mixture and try helps us to tailor their charac- ter cake of clay forms as the water
the collector causes the mineral teristics to fit the task. is drawn off. The structure of the
particles to adhere to the bubbles clay layer depends on the degree of
Clays are also used as drilling
so that they can be recovered at the dispersion of the clay suspension.
fluids in water well and petroleum
surface. The efficiency of this proc-
well production. They are called
ess depends upon the degree of 35
drilling muds and are chemically
adsorption between the collector
and the mineral and can be con-
conditioned to vary their proper- Zeta Potential, mV 30
ties during drilling. A highly
trolled by the zeta potential of the
charged suspension is desirable for 25
particles. In another interesting
the initial drilling operation. This
application, zeta potential studies 20
keeps the clay colloids discrete, al- Zeta
have been used to minimize the Potential
lowing them to penetrate into the 15
viscosity of coal slurries.
porous wall of the drilled hole and
clog the soil pores, forming a thin, 30

Apparent Viscosity
+50 240 impermeable cake which prevents Apparent
Subsidence 220
Viscosity
the loss of drilling fluid. Later, the
Subsidence Time, sec

20
+40 Time
200
clay charge may be reduced to form
+30 180
160
a flocculated suspension in order 10
Zeta Potential, mV

+20 140 to keep it from clogging the lower,


120 pumping zone of the well. 0
+10 Zero Point 0 1 2 3 4 5 6 7 8
of Charge 100 pH
0 80

-10 Control of Slip Casting


Determining Point of Zero Charge Clay suspensions for slip casting must
-20 have their viscosity minimized so that
Zeta These experiments with alpha-alumina
-30 show good correlation between the they pour readily and release trapped
Potential
point of zero charge as determined by air bubbles easily. The above figure
-40
zeta potential and the point of maxi- shows the effect of pH on the apparent
mum subsidence rate. Subsidence viscosity and zeta potential of thoria
-50
8.5 9.0 9.5 10.0
rate is a measure of the degree of (ThO3). Note that a maximum zeta
pH potential corresponds to a low appar-
coagulation.
ent viscosity.

6
Coal Dyestuffs
Dairy Products Emulsions
Detergents Fibers
Dry Powder Technology

Pharmaceuticals 250 Paints


The physical properties of a +40 200 The pigments in paint must be

Relative Viscosity
Relative
pharmaceutical suspension affect Viscosity well dispersed in order for the paint
+30 150
the user’s response to the product. to perform successfully. If the pig-
A successful suspension will not Zeta Potential, mV ment agglomerates, then the paint
+20 100
cake and will, therefore enjoy a will seem to have larger pigment
+10 50
long shelf life. With fine colloids particles and may fail color qual-
this can be achieved by adding a 0 0 ity. Gloss and texture are also af-
suspending agent to increase the fected by the degree of dispersion
zeta potential, and produce maxi- -10 Zeta between the particles in the paint.
Potential
mum repulsion between adjacent Zeta potential measurements can
-20
particles. This highly dispersed be used in this application to con-
system will settle very slowly, but Optimum ZP trol the composition of the paint
-30
any that do settle will pack tightly 0.0 0.5 1.0 1.5 2.0 2.5 3.0 and the dosage of additive required
and aggravate caking. Carrageenan, % for an optimum dispersion.
Another, and sometimes more Fluidization of an Antacid
effective, approach is to formulate Suspension
a weakly flocculated suspension. Fluidization is an alternative to
The suspended particles form light, flocculation. A negatively charged
fluffy agglomerates held together colloidal polyelectrolyte is used as a
by van der Waals forces. The floc- “fluidizing” agent. The polyelectrolyte
adsorbs onto the surfaces of insoluble
culated particles settle rapidly
particles and deflocculates them once
forming a loosely adhering mass the zeta potential exceeds the critical
with a large sediment height in- value.
stead of a cake. Gentle agitation
This graph illustrates the fluidization of
will easily resuspend the particles. an aluminum hydroxide suspension
Weak flocculation requires a zeta using carrageenan sodium as the
potential of almost zero. “fluidizing” agent. The drops in zeta
potential and viscosity of the suspen-
sion correlate quite well with each
other and are produced by an increase
in the concentration of carrageenan.

Zeta-Meter Inc. 7
Foods Petroleum
Latex Production Photographic Emulsions
Petrochemicals Pigments

Water and Wastewater Papermaking +20

Zeta Potentail, mV
Optimum
Coagulation Retention of fines and fibers can +10 ZP Zeta
Potential
Zeta potential is a convenient be increased through zeta poten- 0
way to optimize coagulant dosage tial control. This reduces the
-10
in water and wastewater treat- amount of sludge produced by the 100

ment. The most difficult suspended wastewater treatment facility as -20


well as the load on white water 80
solids to remove are the colloids.

Size Retained, %
-30
Due to their small size, they easily recycle systems. Zeta potential
60
escape both sedimentation and fil- measurements also assist the pa-
tration. The key to effective colloid permaker in understanding the Size 40
removal is reduction of their zeta effect of various paper ingredients Retained
potential with coagulants, such as as well as the physical characteris- 20
alum, ferric chloride and/or cati- tics of the paper particles them-
onic polymers. Once the charge is selves.
0 0.1 0.2 0.3 0.4 0.5 0.6
reduced or eliminated, then no re- % Polyamine Resin
pulsive forces exist and gentle agi-
tation in a flocculation basin causes Synthetic Size Retention in Paper-
making
numerous successful colloid colli-
The point of maximum size retention
sions. Microflocs form and grow corresponds to a zeta potential of +4,
into visible floc particles that settle which can be considered the optimum
rapidly and filter easily. ZP. More positive or more negative
values of the zeta potential cause a
Zeta Potential Control of Alum Dose drop in the percent of size retained.
There is no single zeta potential that Operating at the optimum value results
will guarantee good coagulation for in titanium oxide savings, improved
+5 Zeta every treatment plant. It will usually be sheet formation, increased wire life,
Potential between 0 and -10 mV but the target improved sizing, pitch control, and
value is best set by test, using pilot biocide reduction.
Turbidty of Finished Water, NTU

0 0.5
plant or actual operating experience.
Zeta Potentail, mV

Once the target ZP is established, then


-5 0.4 these correlations are no longer
necessary, except for infrequent Order a Catalog
checks. Just take a sample from the Our catalog describes our instru-
-10 0.3
rapid mix basin and measure the zeta ments and accessories in depth,
potential. If the measured value is and will help you select the
-15 0.2 more negative than the target ZP, then appropriate configuration.
Turbidity increase the coagulant dose (and vice-
versa). Zeta-Meter, Inc.
-20 0.1 In this example a zeta potential of -3 765 Middlebrook Avenue
mV corresponds to the lowest filtered PO Box 3008
-25 0.0
water turbidity and would be used as Staunton, VA 24402, USA
10 20 30 40 50 60 the target ZP.
Alum Dose, mg/L
Telephone ............... 540-886-3503
Toll-Free (USA) ....... 800-333-0229
Fax .......................... 540-886-3728

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