Q1.

The surface potential and zeta potential of a colloid are closely related. Surface potential refers to the
electrical potential difference between the surface charge of a colloid particle and that of the
surrounding bulk solution. In solution, an electrical double layer of counterions forms around the surface
charge, dampening the electrical field and reducing the electrical potential as distance from the particle
increases. The zeta potential, measured at the shearing plane of the double layer, measures the
remaining potential from the surface charge after the dampening effect of the double layer. The
strength of the zeta potential is therefore directly related to the strength of the surface potential, and a
larger surface potential will result in a larger zeta potential.[1-2]

Q2.

Experimental data for the Hamaker constants of Au-Au or SiO2-SiO2 interactions in water is limited and is
instead often theoretically deduced. This can be done from experimental Hamaker constants for Au, SiO 2
and H2O in a vacumn, which are:

A[Au] = 45 x 10-20 J [3]

A[SiO2] = 7.2 x 10-20 J [3]

A[H2O] = 4.8 x 10-20 J [3]

The combining relations law[1] can be used to approximate an effective Hamaker constant for a material
in a medium as follows:

Aeff =( √ A1− √ A M )
2

Where Aeff is the effective Hamaker constant, A1 is the Hamaker constant for material 1 in a vacumn, and
AM is the Hamaker constant for material 2 (i.e. the medium) in a vacumn. Therefore:

For Au - Au interactions in H2O:

Aeff = 2.0 x 10-19 J

For SiO2 - SiO2 interactions in H2O:

Aeff = 2.4 x 10-21 J

Q3.

ε r ( 80℃ )=62.3 F/m[4]

ε r (30 ℃ )=78.4 F/m[4]

ε r (15 ℃ )=82.1 F/m[4]

ε r ( 0℃ )=87.8 F/m[4]
Q4.

Figure 1 – Net force for Au-Au particle interactions in water, as a function of particle
separation.

Figure 2 – Net force for SiO2-SiO2 particle interactions in water, as a function of particle
separation.

Both graphs have a similar relationship, where at a large distance there is little interactive force between
particles. This continues as particle separation decreases, and both graphs are dominated by repulsive
forces between the particles When the separation becomes very small, and a sharp change occurs
where the interaction is dominated by attractive forces. The differences are that the Au graph becomes
dominated by attractive forces at a larger separation distance, and the repulsive energy barrier that
prevents particle aggregation is much smaller for Au than SiO2.

Because the SiO2 graph shows a much larger repulsive energy barrier preventing particle aggregation,
the SiO2 colloid will be more stable than the Au colloid.
Q5.

The Au NPs are certain to collapse at a zeta potential of <28 mV and the SiO2 NPs are certain to collapse
at <11 mV. At these zeta potentials, there is no longer a net repulsive force to act as an energy barrier
between the aggregation of particles. It is possible these particles are still unstable at even higher zeta
potentials because collision energy of particles could overcome even a small repulsive energy barrier. [5]
However, it is hard to determine the zeta potential at which this stops without knowing the collision
energy.

This variation in stability is largely resultant from the difference in the Hamaker constants between Au
and SiO2, which stems from the stronger Van der Waals interactions between Au particles compared
SiO2 particles.[3] Because all other parameters remain constant, the repulsion component of the net
particle interaction remains the same for both materials. However, the attraction component of the net
particle interaction will be larger for Au due to the larger Hamaker constant. Therefore, an Au colloid
requires a higher repulsive force (and hence zeta potential) to counteract aggregation and remain
stable.[3]
[1] Israelachvili, J. N. (2011). Intermolecular and surface forces (3rd ed.). Academic Press.

[2] Mulvaney, P. (2001). Metal Nanoparticles: Double Layers, Optical Properties, and Electrochemistry. In
Nanoscale Materials in Chemistry (pp. 121–167).
https://doi.org/https://doi.org/10.1002/0471220620.ch5

[3] Xu, J. Q., Chen, L. Y., Choi, H., & Li, X. C. (2012). Theoretical study and pathways for nanoparticle
capture during solidification of metal melt. Journal of Physics: Condensed Matter, 24(25), 255304.
https://doi.org/10.1088/0953-8984/24/25/255304

[4] Chistyakov, A. D. (2007). The permittivity of water and water vapor in saturation states. Russian
Journal of Physical Chemistry, 81(1), 5–8. https://doi.org/10.1134/S0036024407010025

[5] Tsai, D. H., Pease III, L. F., Zangmeister, R. A., Tarlov, M. J., & Zachariah, M. R. (2009). Aggregation
Kinetics of Colloidal Particles Measured by Gas-Phase Differential Mobility Analysis. Langmuir, 25(1),
140–146. https://doi.org/10.1021/la703164j