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Inform is a series of white papers designed to

provide advice on material characterization issues


10 ways to...
Control rheology by changing
particle properties (Size, Zeta
potential and Shape)
Many materials in use today are disperse systems where one substance
(often particulate) is dispersed in another phase. These material types
include adhesives, agrochemicals, cement, ceramics, colloids, cosmetics
and personal care formulations, food and drink, mining and mineral
slurries, paints, inks and surface coatings, pharmaceuticals and polymer
systems.
For example:-
In the inks industry, the understanding of rheology and particle properties
allows solid pigment content to be changed in different formulations whilst
maintaining the critical rheological characteristics required for optimised
printing.
In the cement industry, the understanding of rheology and particle
properties, such as the aggregate morphology, allows ow behaviour
during processing and application to be controlled.
In the Cosmetics and Personal Care industries, it is essential to understand
the relationship between rheology and particle properties to provide the
optimum balance in terms of formulation, consumer acceptance and
application performance.
The physical properties of the dispersed particles, such as the average
particle size, the size distribution, the zeta potential or charge on the
particles and even the shape of the particles all help inuence the overall
(bulk) materials properties such as the rheology.
This Ten Ways guides you through some of the fundamental properties of
the dispersed system, and demonstrates how these affect the rheological
properties. Whereas it in interesting to understand the bulk material
properties, such as rheology, which are associated with the changes
in the particle size, shape and zeta potential, these examples will also
demonstrate that this understanding allows the rheology of the material to
be controlled.
For a constant volume fraction, when the particle size is decreased, the
number of particles increases. Therefore, the number of particle-particle
interactions increases, so the viscosity of a sample typically increases. As
particle-particle interactions are weak forces, the effect is seen more at low
shear rates.

Decrease the particle size and the viscosity generally increases.
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Ten Ways to..Control Rheology by Changing Particle Properties
Conversely, if the particle size is increased, this leads to a smaller number
of particle-particle interactions. Again, due to the weak nature of this
association, the effect is seen most dramatically at low shears.

Increase the particle size and the viscosity generally decreases.
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Particles which have a wide span / distribution (large polydisperity) tend
to pack better than a system of particles of all the same size (a narrow
distribution). This basically means that a wide distribution of particles has
more free space to move around, which therefore means it is easier for
the sample to ow, i.e. a lower viscosity. So, tightening up the particle
distribution can increase the stability of a system.
For example, on keeping the volume fraction the same, a sample of
relatively large particles with a small proportion of small particles will have a
viscosity lower than either the small particles or large particles alone.
This is basically due to the two competing effects of changing the number
of particle-particle interactions on changing the size and also changing the
polydispersity. Both affect the viscosity, however, in this case, the effect of
polydispersity dominates at one particular ratio.
The effect on the viscosity of particle size and particle size distribution can be
used in combination for some interesting effects.
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Increase the particle size distribution (span) and the viscosity decreases.
3
Ensuring the particle size is constant, where more and more particles are
introduced the ow behaviour will generally go from Newtonian (so few
particles that they do not interact with each other), to shear thin (now the
particles can interact, but the forces are so small that this interaction can
be broken down with an increasing shear rate, therefore a shear thinning
property), to shear thickening (where there are so many particles that on
increasing the shear rate the particles now start to physically collide with
each other which causes a shear thickening effect).
Increasing the number of particles in a system to change the ow
behaviour.
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As the zeta potential is increased, the particles are forced to stay away
from each other. This is basically preventing the particles from owing
freely, hence the viscosity increases. The effect is seen more at lower shear
rates as this is a small force.
For larger particles, the settling force of gravity on the particles will
overcome any repulsion of the particles due to the electrostatic charge
/ zeta potential. However, as these large particles can no longer fully
aggregate (hydration layer), this close range, yet strong, Van der Waals
attractive force can increase the low shear viscosity.
For particles greater than a micron, i.e. dispersions, (where gravity now has a
signi cant effect) at high concentration, decreasing the zeta potential towards
the iso-electric point to take advantage of the secondary minimum can
create a self supporting gel system to introduce a yield stress to the system.
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For particles smaller than a micron, i.e. colloids, increasing the magnitude of
the zeta potential (either +ive or ive) increases the lower shear viscosity.
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Smooth particles have a resistance to move as there is typically an
association between the different particles, which is often a chemical
interaction. However, with non-smooth particles there will also be
a mechanical resistance, and also the chemical association can be
increased. Therefore, non-smooth particles have higher low shear viscosity
and a higher yield stress.
Smoother particles have a lower low shear viscosity than those
which are sharp/non-smooth (i.e. a lower convexity).
8
With spherical particles, there are typically particle-particle interactions
which break down under shear to give a shear thinning behaviour.
However, with elongated particles the random orientation leads to a higher
barrier to start ow; an increase in low shear viscosity. However, under
shear, these elongated particles can orient themselves to be streamlined
with the direction of ow. They are therefore easier to ow, resulting in a
lower shear viscosity than the spherical same size equivalent.
With soft particles, a forced shear can change the shape of the particle.
This can lead to the particles elongating and aligning under shear resulting
in a more shear thinning system.

Particles which are elongated tend to have a higher low shear viscosity but
a lower high shear viscosity than their more spherical size equivalents.
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With particles of the same size, soft/deformable particles tend to have a
more shear thinning behaviour than their hard/rigid equivalents.
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2009 MRK1236-02
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We hope you find Ten Ways to..
Control Rheology by Changing Particle
Properties useful.
This is one in a series of publications
designed to help decision makers in your
industry make more informed choices.