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The Applications of Zeta Potential in Process Control

Author: Matthew Cantelo

This work by Ceram is licensed under a Creative Commons AttributionNonCommercial-ShareAlike 3.0 Unported License

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Introduction
Powders play a very important role in many different areas of healthcare, most importantly in dentistry and orthopaedic materials, where they become either coatings or 3D structures. As many powder materials exist as suspensions in the early stages of their manufacturing, powder surface chemistry (and associated charge) can strongly influence suspensions’ rheological properties, and so the quality of subsequent processing. This can have dramatic effects on the quality of any endproducts and can lead to failure of these products. Given that powder surface charge is so critical, zeta potential becomes a crucial measurement for characterising and then optimising suspension behaviour. Zeta potential is essentially the energy required to shear a particle and associated ions away from a bulk solution. From these values, the stability of the system can be established: whether the particles are well dispersed and stable, or flocculated and unstable. This paper will discuss the theory of zeta potential, and how it can be measured and controlled. The particular advantages of using the ZetaProbe® apparatus available at Ceram will also be discussed.

Zeta Potential – The Theory
All inorganic particles will form a surface charge when dispersed in a liquid, typically water for industrial applications. Depending on the nature of the material, this charge can be positive or negative. For example, silica particles will form a negative charge in water as the surface Si-OH bonds present are deprotonated: Si-OH + H2O  Si-O- + H3O+ The hydroxonium ions in the solution will make the solution acidic, and in addition, partly reduce the negative surface charge by reacting back into the surface to reform Si-OH. Conversely, alumina particles in water are protonated, which releases the residual negative OH- ions into the solution and makes it more basic. Al-OH + H2O  Al-OH2+ + OHThese behaviours arise from the different pKa values between alumina and silica. The charged particle surface attracts electrolyte ions of opposite charge. These ions form the so-called double layer (see figure 1); initially a tightly bound layer of oppositely charged ions becomes strongly attracted to the surface (the Stern layer). The layer does not completely offset the surface charge on the particle however, as the charge contribution from the ionic radius of the particle is much larger than the contribution from the surface chemistry. Thus a more diffuse second layer forms. This layer contains a mixture of both positive and negative ions, but the counter-ion charge still dominates. Eventually, at a specific distance from the particle (the shear plane), the surface charges become balanced, and beyond the outside of this double layer the bulk solution contains equal amounts of positive and negative particles. Zeta potential is defined as the energy required to shear a particle and its associated double layer away from the bulk solution, as shown in figure 1. It is measured in millivolts (mV) and can be positive or negative. A large zeta potential (± 50 mV) is indicative of a stable system, where the particles are well dispersed and there is minimal flocculation. A low zeta potential (± 10 mV) indicates an unstable system,
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where there is lots of flocculation occurring and the particles are not properly dispersed. A value of ±25 mV is considered to be the minimum for a stable system.
ΖETA POTENTIAL BOUNDARY

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Stern layer

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Figure 1 – The Stern Model of the Electrochemical Double Layer

The size of the double layer associated with the particle is important when determining zeta potential. If a particle has a large double layer, it will not be able to get close to other particles in the suspension due to the electrostatic repulsions between the ions in approaching double layers. This will give a large zeta potential and a more stable suspension. If the double layer is smaller, the van der Waal’s attractive forces dominate. The magnitude of the zeta potential can have a large effect on other properties of the suspension, especially the rheological properties. Rheology is a measurement of how viscous a material is, measured in terms of shear stress and shear strain. A system with a high zeta potential has a low degree of flocculation, and this will give a very low viscosity as the particles are separated from each other throughout the solution, allowing plenty of opportunity for the aqueous phase to flow between particles and provide fluidity. Conversely, a system with a low zeta potential will have a lot of flocculated particles that take up most of the water in the connected structures. Therefore, there is less ‘free’ water available to provide fluidity and a more viscous suspension results. Interestingly, a highly deflocculated suspension is not always desirable: whilst useful in maximising solids loadings and minimising high shear viscosity ahead of spray drying, casting of a slip often requires a degree of structure arising from particle-particle interactions in a mildly flocculated system (see figure 2).

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Measuring Zeta Potential
There are several different methods available for measuring zeta potential, but an approach that is common to all is to measure it against pH. As the pH of the solution varies, the amount of acid or base present in the system will alter the surface chemistry of the particles. For example, adding enough acid to silica will return it eventually to Si-OH and then Si-OH2+, and adding enough base to alumina will eventually generate Al-O-. On a zeta potential vs pH graph, the curve usually passes through a point where mV = 0, which is known as the isoelectric point. However, different powder chemistries will result in a finger-print graph. Figure 3 shows a typical zeta potential vs pH curve for a zirconia suspension, a material widely used in medical devices, especially in the field of dentistry2.

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In a highly charged system, the particles repel each other as they all have the same high surface charge, and become well dispersed in the suspension. The intermolecular attractive forces are low, and repulsive ones are high.

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In a poorly charged system, as the surface energy is greater than the electrostatic repulsions between the particles, some will attract each other and aggregate, leading to a poorly dispersed suspension. The intermolecular attractive forces are high, and the repulsive ones low. Figure 2 – Intermolecular Forces in Dispersions

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Figure 3 – A Typical Zeta Potential vs pH Curve

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One of the earlier methods of measuring zeta potential used electrophoresis. In this procedure, a direct voltage is supplied to the sample suspension and particle movement towards the electrode is monitored. Particle movement is usually quantified by light scattering measurements. However, this approach requires very dilute suspensions that are not typical of those encountered in industry and are very sensitive to contamination as there are so few particles in the suspension. The ion equilibrium must be kept the same in order for the results to be accurate, and this is very difficult to do in practice. Also, above 5µm, sedimentation may occur between the particles, which is undesirable. Ceram employs apparatus that takes advantage of a phenomenon known as the electrokinetic sonic amplitude (ESA). Alternating (rather than direct) voltage is applied to the suspension, and this causes the particles in the suspension to vibrate as they move backwards and forwards between the two electrodes. This creates a pressure wave in the suspension, which is detected using a pressure transducer. After an initial measurement, acid and base of a known concentration can be accurately titrated into the suspension in increments to perform a zeta potential vs pH sweep. The accompanying software to this apparatus allows the user to enter a desired starting pH of the system, and then automatically titrate (at defined pH increments) between set pH points, typically pH3 to pH11, to give the zeta potential values at various pH levels. This gives the characteristic curve shown in figure 3. The ESA can be affected by many factors, including acoustic impedance, particle volume fraction and density, solvent density, instrument factors, and dynamic mobility, which is a combination of particle size and zeta potential. Mathematics in the software can deal with these variables such that ESA can be calculated for any system as long as the particle dielectric constant, concentration, and density of the particles and solvent being measured are known.

Controlling Zeta Potential
Frequently, clients discover that their powder suspensions have variable properties and/or lead to poor yields and poor end-product properties downstream. Ceram can quantify suspension problems using rheology and zeta potential. Since control of zeta potential lies at the root cause of poor suspension, changing it is paramount. Fortunately, zeta potential can be altered and controlled through the addition of other types of chemicals, most importantly electrolytes and surfactants. Electrolytes, for example Na+, K+ and Ca2+, can compress the double layer in systems where the
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surface of the particles is negatively charged. The charge on the electrolytes helps balance the charge on the surface of the particles more efficiently, and this double layer compression will increase as the charge on the electrolyte increases, so Ca2+ will have more effect than Na+. This reduction in double layer thickness is normally accompanied by an increase in flocculation, which in some systems is necessary. Using surfactants is another highly effective way to control the zeta potential of a suspension. Surfactants are surface active agents; molecules that attach to the surfaces of particles in suspension and therefore dictate surface chemistry. There are three different families of surfactants that are in common use: electrostatic, electrosteric, and steric. Steric surfactants have very long chains as part of their structure – they are often carbon-based polymers, and are non-ionic. These larger molecules will give rise to larger particles in the suspension, preventing any other particles interacting with each other and forming aggregates. An example of a steric surfactant is polyethylene glycol, which is a polymer of ethylene oxide that can obtain a molecular weight of up to 100,000 Daltons. Steric surfactants have no impact on zeta potential. Electrostatic surfactants on the other hand may not be anywhere near as large and bulky as steric surfactants, but instead use charged groups (these can be positive or negative) to influence powder surface charge when adsorbed. Tiron, a surfactant molecule based on benzene, is an example of an electrostatic surfactant. The third group of surfactants combines both the bulky steric parts of the molecule and the ionic electrostatic parts, and these are called electrosteric surfactants. Polymethyl methacrylates, with their free carboxylic acid functionalities, are examples of electrosteric surfactants.

Conclusions
Zeta potential is a very useful analytical method for investigating the properties of powder suspensions, and can give a wealth of information about the surface chemistry and subsequent interactions between the particles. It can be used to optimise processing methods and as a quality control method, both of which are extremely important for the ceramic sector and for industry as a whole. The next white paper in this series will apply this information about measuring zeta potential and its effects to the medical materials manufacturing sector.

References
1. 2. 3. An Introduction to Interfaces and Colloids, J.C. Berg, ISBN 9814299820 P. Papaspyridakos, K. Lal (2008), Journal of Prosthetic Dentistry 100 (3) 165– 172 Work undertaken at Ceram in December 2012 for a client, investigating the zeta potential of zirconia samples.

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About Ceram
Ceram is an independent expert in innovation, sustainability and quality assurance of materials. With a long history in the ceramics industry, Ceram has diversified into other materials and other markets including aerospace and defence, medical and healthcare, minerals, electronics and energy and environment. Partnership is central to how we do business; we work with our clients to understand their needs so that we can help them overcome materials challenges, develop new products, processes and technologies and gain real, tangible results. Headquartered in Staffordshire, UK, Ceram has approved laboratories around the world.

About the Author
Matthew Cantelo Laboratory Chemist Matthew Cantelo has a MChem (Hons) chemistry degree from Cardiff University. His final year research project was largely focused on inorganic synthesis within healthcare applications. This is an area that Matthew is continuing to concentrate on at Ceram, particularly with regards to hydroxyapatite synthesis.

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