A48IP010EN-A THE ZETA Guide 2014

The ZETA Guide
Principles of the streaming potential technique
Thomas Luxbacher
The Zeta Potential for
Solid Surface Analysis
A practical guide to streaming

potential measurement
1 st edition
by
Thomas Luxbacher
Copyright © 2014 Anton Paar GmbH, Austria.
All rights reserved. No part of this publication may be

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Date: March 2014
Specifications subject to change without notice. | A48IP010EN-A

Preface
The zeta potential and its application in colloid chemistry is dis-
cussed in a variety of textbooks. Although the theoretical back-
ground of the zeta potential is the same regardless of whether it
is applied for colloid or solid surface characterization, a different
approach is required to understand the zeta potential in the field of
solid surface analysis. The lack of a comprehensive textbook for the
zeta potential in solid surface analysis was the motivation for writing
this practical guide. It is meant to help people who are new to the
field of zeta potential analysis for solid surface characterization. It
further aims to be a state-of-the-art guide to the streaming poten-
tial method, which is the experimental approach to determining the
zeta potential for solid surfaces.
Graz, March 2014 Thomas Luxbacher

Contents
1. Introduction 9
2. Historical background 11
3. The zeta potential 12
3.1. Surface charge formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

3.2. Electrokinetic phenomena. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4. The streaming potential technique 20
4.1. Zeta potential calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

4.2. Material and interfacial conductance. . . . . . . . . . . . . . . . . . . . . . 31
5. Instrumentation 35
5.1. Measuring cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
6. Dependences of the zeta potential 42
6.1. pH value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
6.2. Ionic strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.3. Additive concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
6.4. Size. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
6.5. Porosity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.6. Electronic conductance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
6.7. Surface roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6.8. Measuring time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
6.9. Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6.10. Material swelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
7. Measurement capabilities 72
7.1. Zeta potential. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

7.2. Isoelectric point. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
7.3. Adsorption analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.4. Simulation of environmental conditions. . . . . . . . . . . . . . . . . . . . 83
8. Applications 86
8.1. Membranes and filters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

8.2. Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.3. Semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
8.4. Natural and man-made fibers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
8.5. Cosmetics and detergents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
8.6. Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8.7. Minerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
9. Tips and tricks 111
9.1. Air bubbles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

9.2. How does carbon dioxide affect the zeta potential?. . . . . . . . 113
9.3. Asymmetric sample mounting . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
10. Outlook 121
11. References 123

Introduction
1. Introduction
You have presumably first learnt about the zeta potential in courses
on physical chemistry or related subjects. The information about
the zeta potential was probably linked to colloidal systems such
as particle dispersions or emulsions. The zeta potential was hardly
ever referred to as a parameter for solid surface analysis. This
lack of general reference is astonishing, since the surface zeta
potential has a long history. The electrokinetic effects of electro-
osmosis, streaming potential and electrophoresis were discovered
in the middle of the 18 th century (see chapter 2 for the histori-
cal background). At the beginning of the 19 th century the relations
between these effects and the zeta potential were investigated.
Initial research focused on fibrous systems using the streaming
potential approach. This method then fell into oblivion until the late
1980s, when the concept of the streaming potential was re-visited
and the first instrument for analyzing the solid surface zeta poten-
tial became commercially available.
Why is the zeta potential relevant? In particle suspensions and

liquid-liquid emulsions, the zeta potential determines the dispersion
stability. As a rule of thumb, a zeta potential of ± 25 mV and above
describes a stable dispersion (i.e. the coagulation of its particles or
emulsion droplets is highly unlikely). This stability analysis is cer-
tainly not applicable to the solid surface zeta potential. Although
based on the same theoretical background (but on a different
physical principle), the zeta potential has a different meaning when
applied to the analysis of macroscopic solid surfaces. The main
focus of the zeta potential analysis is information on the surface
charge. This charge, which is established on the surface of a solid
material in contact with water, determines the behavior of the
material in processes where aqueous systems play a role (such
as membranes for water treatment, biomaterials in contact with
blood, wet processing of semiconductor wafers, mineral flotation,
etc.). Electrostatic attraction and repulsion are driven by the sur-
face charge (among other things) and thus by the solid surface
zeta potential. Furthermore, the zeta potential provides information
9
Introduction
about surface functionality (carried by chemical groups that inter-

act with a surrounding aqueous solution in a specific manner), the
specific interaction of dissolved compounds with the solid surface,
and liquid-on-solid surface adsorption processes.
Which knowledge is required to read zeta potential results

correctly? The theoretical background of the zeta potential (both
for macroscopic solid surfaces as well as for particle dispersions)
combines the classical equations for charge density, ion distri
bution and hydrodynamic flow. The zeta potential theory thus
appears rather complex; however, for its practical application, an
understanding of aqueous chemistry (acid, base, pH) and – at least
for the solid surface zeta potenial – the basic physics of electricity
(voltage, current, resistance) is sufficient. This guide is therefore
mainly focused on the practical aspects of the zeta potential for
solid surface analysis.
After a brief review of the historical development of the zeta poten-

tial theory (chapter 2) the electrokinetic effects are introduced in
chapter 3. These effects are used to determine the model para
meter of zeta potential and thus the surface charge for various
systems. The streaming potential, which is the electrokinetic
effect for the determination of the solid surface zeta potential, is
addressed in chapter 4. The development of measuring instru-
ments and dedicated sample holders is illustrated in chapter 5.
The zeta potential is an interfacial property and thus depends on
the functiona lity of the solid surface and on the composition of the
aqueous solution. The various dependences of the zeta potential
are described in detail in chapter 6. Instead of being unsettled,
we use these dependences to gain additional information about
surface properties such as porosity, swelling, or electrical con
ductance. In chapter 7 we take a look at the different approaches
of the zeta potential for solid surface analysis. Chapter 8 gives an
overview of fields of applications of the solid surface zeta potential
with selected examples that should illustrate the possibilities
offered by the streaming potential method.
10
Historical background
2. Historical background
In 1809 Ferdinand Friedrich Reuss observed the migration of
colloidal clay particles when an electric field was applied to the
solution (electrophoresis) as well as water flow through a plug of
clay upon the application of voltage (electro-osmotic flow). Reuss
thus set the foundation for the discovery of the electrokinetic
effects. It was Georg Hermann Quincke who described the stream-
ing potential for the first time in 1859.
The development of an appropriate model was essential for the

understanding of the observed electrokinetic effects. In 1879
Hermann von Helmholtz set the foundation to the electric double
layer theory. He described a correlation between the streaming
potential and the electrical potential difference at the solid-liquid
interface. Jean-Baptiste Perrin denoted this interfacial potential as
the electrokinetic potential (1904), which was given the Greek letter
ζ and renamed as zeta potential by Freundlich in 1924. Marjan von
Smoluchowski refined von Helmholtz’ correlation in 1905. The
Helmholtz-Smoluchowksi equations for the calculation of the zeta
potential are still employed today. Smoluchowski was also the first
to draw attention to the important phenomenon of the surface con-
ductance.
G. H. Quincke H. v. Helmholtz M. v. Smoluchowski

(1843-1924) (1821-1894) (1872-1917)
For more detailed information about the history of electrokinetics

refer to the review articles by Lyklema (2003) and Wall (2010).
11
The zeta potential
3. The zeta potential

The zeta potential, a.k.a. the electrokinetic potential, describes the
charging behavior at interfaces. The majority of scientific papers
and practical applications use and report the zeta potential for the
characterization of the solid-liquid interface. The zeta potential has
also gained importance for the understanding of the stabilization of
emulsions (liquid-liquid interface) and foams (liquid-gas interface).
The solid-liquid interface is the main focus of this booklet.
The charging behavior at the solid-liquid interface and the defini-
tion of the zeta potential are explained using the model of the elec-
trical or electrochemical double layer (EDL) shown in Figure 3.1.
Fig. 3.1.
Model of the
electrochemical
double layer at the
solid-liquid inter-
face (ΨS…surface
potential, ζ…zeta
potential)
In contact with an aqueous solution, a solid surface assumes a

surface charge. The charged solid surface provokes an interfacial
charge distribution that is different from the charge distribution in
the liquid phase. The surface charge gives further rise to a surface
potential, which decays with increasing distance from the solid sur-
face. The EDL model distinguishes between a stationary immobile
and a diffuse mobile layer of counterions that compensate the sur-
face charge.
12
The zeta potential
This so-called Stern model of the EDL may be extended by a sub-

structure of the stationary layer, i.e. the inner and outer Helmholtz
planes. Since the zeta potential is defined as the potential at the
outside of the stationary layer, its sub-structure may be neglected.
Common to all models is the existence of the zeta potential at
the boundary between the stationary layer and the diffuse layer of
counterions, which is accessible experimentally by measuring any
of the electrokinetic effects (see chapter 3.2) that are appropriate
for the solid sample. The boundary is known as the “shear plane”
and indicates the location of slipping of the moving liquid phase
relative to the stationary liquid phase during the electrokinetic
measurement. Its location off the solid surface is responsible for
the zeta potential as an interfacial property and depends on both
the surface potential (surface charge) and the properties of the
liquid.
Eq. 3.1 relates the zeta potential ζ to the electrokinetic charge

density σ ek, i.e., the number of charges per unit area that are pres-
ent at the plane of shear of the solid-liquid interface (Lyklema,
2001).
Eq. 3.1
ε 0 is the vacuum permittivity, ε r is the dielectric coefficient of the

liquid, R is the gas constant, T the absolute temperature, c the sol-
ute concentration in the liquid, and F is Faraday’s constant.
ζ The zeta potential is a parameter which describes the

charging behavior at the solid-liquid interface.
The model of the electrochemical double layer defines

the zeta potential as the electrical potential at the “shear
plane” which separates a stationary layer and a mobile
layer of charges.
13
The zeta potential
 3.1. Surface charge formation
The surface charge at the interface between a solid material and an

aqueous solution is generated by two major mechanisms:
• acid-base reactions between surface functional groups and an

aqueous solution
• and the adsorption of water ions.
Among these dominant contributions to the surface charge, an

important consideration for mineral surfaces is ion dissolution from
a crystalline lattice.
Charge formation by reaction of surface functional groups
Figure 3.2 schematically shows the interaction of acidic and basic

functional groups with water molecules.
Fig. 3.2.
Schematic
presentation of
charge formation at
the solid-liquid inter-
face for a hydrophilic
material surface
with acidic or basic
functional groups
Acidic groups such as carboxylic acid, sulfonic acid or hydroxyl

groups dissociate in water and remain negatively charged. Basic
groups such as primary, secondary and tertiary amine groups get
protonated and assume a positive charge. The surface charges
generated by acid-base reactions are linked to the functional
groups that are chemically bound to the surface.
14
The zeta potential
The equilibrium of the surface charging process depends on

the area density of surface functional groups and the pH of the
aqueous solution. A high surface group density may inhibit com-
plete dissociation of acidic groups or protonation of basic groups
due to the electrostatic repulsion between a charged group and
its neighbors. The pH of an aqueous solution is the driving force
for the acid-base reaction. A high pH will enhance the dissocia-
tion of acidic groups but suppress the protonation of basic groups
and vice versa. The pH dependence of zeta potential is therefore
important to retrieve information about the type and strength of
the functional groups present on the solid surface. The pH depen-
dence of zeta potential is discussed in chapter 6.1.
Charge formation by adsorption
For surfaces without functional groups we also find a zeta poten-

tial and thus an interfacial charge. However, the charging behavior
differs from the acid-base reactions of acidic and basic groups.
In aqueous solutions, material surfaces without functional groups
behave hydrophobically. As indicated in Figure 3.3., water
molecules are affected by the presence of a hydrophobic surface
and get replaced by water ions (hydroxide, OH –, and hydronium,
H 3O +).
Fig. 3.3.
Schematic presenta-
tion of charge forma-
tion at the solid-liquid
interface for a hydro-
phobic material
surface without
functional groups
15
The zeta potential
There is still a debate in the scientific world about how to explain

the formation of a “virtual” surface charge. One theoretical
approach predicts that hydroxide ions behave more hydrophobi-
cally than hydronium ions or water and preferably substitute water
molecules at the hydrophobic surfaces.
The other model explains the charging behavior at a hydrophobic

solid-aqueous solution interface by a polarization effect of the solid
surface on the water molecules, which then behave more acidic.
For both models the sign and number of surface charges depend on
the pH of the aqueous solution. At a high pH we find an increased
concentration of OH – ions, which render the surface charge nega-
tive, at a low pH the concentration of H 3 O + becomes dominant
and the surface is positively charged. When the hydrophobic sur-
face assumes the polarization of the water molecules, the acidity
of the interfacial water increases compared to the bulk water. At a
low pH the dissociation of “acidic” interfacial water is suppressed.
Therefore the charging of hydrophobic surfaces in contact with an
aqueous solution again strongly depends on the pH.
Be it ion replacement or water molecule polarization, the effect on

the electrokinetic charge density and thus on the zeta potential is
the point of interest.
ζ The surface charge at the interface between a solid

material and an aqueous solution is generated by two
major mechanisms: (1) acid-base reactions of surface
functional groups and (2) adsorption of ions.
Due to preferable adsorption of hydroxide ions, hydro

phobic surfaces exhibit a negative zeta potential when
they come in contact with an aqueous solution.
16
The zeta potential
 3.2. Electrokinetic phenomena
The zeta potential is a model parameter that describes the charging

behavior at the solid-liquid interface. The determination of the zeta
potential involves the measurement of an electrokinetic effect,
which depends on the size and type of the solid material. The most
prominent electrokinetic effects (electrokinetic phenomena) are
schematically shown in Figure 3.4.
Fig. 3.4.
Selection of electro-
kinetic effects at a
solid-liquid interface
In general, an electrokinetic effect is observed at an interface

between a solid, liquid or gas phase and a liquid phase. In order to
observe the effect, the two phases have to move relative to each
other (in practice, one of these phases remains stationary while
the other phase moves). The electrokinetic effect is a coupling of a
mechanical and an electrical force where the driving force for the
movement may either be of mechanical or electrical nature.
17
The zeta potential
Electricity causes movement
Electrophoretic mobility, electro-osmotic flow and electrokinetic

sonic amplitude are electrokinetic phenomena where the driving
force is an applied electric field.
A direct current (dc) field is used to motivate charged colloidal solid

or liquid particles immersed in a liquid to move towards the elec-
trode of the opposite sign. Electrophoretic mobility is the velocity
of these particles divided by the electric field strength. Electropho-
resis is currently the most common measuring technique to assess
the zeta potential of colloidal dispersions of particles (suspensions)
and liquids (emulsions). In colloidal dispersions the zeta potential is
a powerful parameter used to predict the dispersion stability.
The same dc field provokes liquid motion through a porous solid

material such as a plug of fibers or coarse particles, or a porous
membrane. The achieved electro-osmotic flow usually only leads
to small changes in the liquid volume on both sides of the porous
solid sample, so electro-osmosis is hardly used for zeta potential
analysis.
The electrokinetic sonic amplitude (ESA) is the ultrasound

response to an alternating current (ac) field applied on a colloidal
dispersion of particles. The ESA effect is one of two electrokinetic
phenomena used for the method of electroacoustics.
Movement causes electricity
Sedimentation potential, streaming potential and colloid vibra-

tion potential are generated by a mechanical force that either acts
on solid particles immersed in a liquid, or on the liquid moving
along the surface of a stationary solid material. The force of gravity
causes sedimentation of particles in a suspension. The moving
charged particles lead to a charge separation along the height of
the container (the cylindrical column in Figure 3.4), which generates
18
The zeta potential
a potential difference. When using a centrifuge, the separation

(sedimentation) of particles is enforced but the small signal and/
or complexity of measurement eliminate the sedimentation poten-
tial as a useful measuring technique for zeta potential analysis in
colloidal dispersions.
The streaming potential is generated by the tangential flow of

liquid across a solid surface. Complementary to electro-osmo-
sis, the streaming potential arises when liquid is pushed through
a porous plug of fibers or granular powder or any other porous
material. The streaming potential method is used for the zeta
potential analysis of macroscopic solid surfaces. Details about the
measuring principle are discussed in chapter 4. Alternatively to the
streaming potential, a streaming current is created by the tangen-
tial liquid flow and related to the zeta potential.
The colloid vibration potential (CVP, not shown in Figure 3.4) is the
electrical response (an ac potential difference) to an ultrasonic
wave applied to a colloidal dispersion. The CVP effect is implied in
a certain type of electroacoustics instruments.
ζ The zeta potential is determined by the measurement of

an electrokinetic effect, which is observed when a solid
and a liquid phase move relatively to each other.
Electrophoretic mobility is used for the zeta potential

analysis in colloids while the measurement of the stream-
ing potential gives access to the surface zeta potential.
19
The streaming potential technique
4. The streaming potential

technique
When streaming an aqueous solution 1 through a capillary system,
an electrical response is generated. Depending on the correspond-
ing measuring electronics, this response may be detected as a dc
voltage (streaming potential) or a dc current (streaming current).
The streaming potential has primarily received attention for various

technological applications. Streaming potentials occur in soils and
rocks (Alkafeef and Alajami, 2006) and are an indicator for the
activity in geothermal systems (Revil et al., 1999). Streaming poten-
tials also arise in biological systems such as soft and hard tissues
(Gross and Williams, 1982).
Fig. 4.1.
Schematic drawing
illustrating the gener-
ation of the stream-
ing potential and the
streaming current. (a)
Equilibrium of charge
at the solid-liquid
interface. (b) Liquid
flow provokes move-
ment of surface-
charge compensated
ions. (c) Streaming
potential measured
at equilibrium
between stream-
ing current (direction
of liquid flow) and
back-current (high
impedance electronic
circuit). (d) Stream-
ing current measured
with low impedance
electronic circuit.
1
The principle of streaming potential and streaming current measurement is also
applicable to non-aqueous solvents. The accompanying processes of ion formation,
electrical conductivity and acidic or basic behavior are little understood and make the
zeta potential analysis more complex. In this book we therefore restrict the discussion
to the analysis of aqueous solutions.
20
The formation of the streaming potential and the streaming current

is illustrated in Figure 4.1.
We start with a capillary between solid surfaces which is filled with

an aqueous solution (a). The capillary may be of irregular shape
(e.g. voids between particles of a powder bed or between fibers
of a fiber plug) or of a regular shape (slit channel between planar
material surfaces). Upon contact of water with the solid material,
a surface charge is generated and immediately compensated by
ions of opposite charge (counterions) in the aqueous solution. An
equilibrium of this electrochemical double layer is a requirement
for a reliable measurement of the streaming potential (for the time
required to obtain such an equilibrium refer to chapter 6.8).
When streaming the aqueous solution through the capillary, shear

forces act on the counterions compensating the surface charge and
move these ions in the direction of liquid flow (b). For the stream-
ing potential measurement, an electronic circuit with a high internal
resistance is used. A charge separation between the inlet and the
outlet of the pressure-determining capillary is thus obtained (c). The
charge separation introduces an electric force that countera cts the
liquid flow. A back-current of charges arises which partially com-
pensates the current of ions in the flow direction. The net charge
separation leads to an electrical potential difference. This so-called
streaming potential is detected between electrodes located on
both ends of the capillary.
For streaming current measurement a different electronic circuit

with a low internal resistance is applied. The flow of the aqueous
solution again shears off the counterions, which are moved towards
the electrode at the outlet of the capillary (d). Moving charges pro-
voke an electric current. At the electrode interface, an ion-electrode
charge transfer takes place and the so-called streaming current is
measured.
The schematic representation of the streaming potential and

streaming current shown in Figure 4.1 makes it obvious that these
21
parameters depend on certain measuring conditions:
• Volume flow rate

• Ionic strength
• Size of flow channel / capillary
The charge separation and thus the streaming potential and the
streaming current depend on the shear rate at the solid-liquid
interface, which is determined by the size of the capillary and the
volume flow rate of the aqueous solution. The higher the flow rate,
the higher the streaming potential and streaming current.
It further becomes obvious that the number of ions present in the

aqueous solution (determined by the ionic strength, solute con-
centration or electrolyte conductivity) affects the formation of the
charge separation and thus of the streaming potential and stream-
ing current signals. At low ionic strength, fewer ions are available
to replace counterions, which are sheared off their equilibrium
position. At higher ionic strength only a small charge separation
is achieved and the electric force introducing the back-current
approaches the mechanical force of the liquid flow.
Last but not least, the geometry of the capillary may affect the
streaming potential and the streaming current. While the streaming
potential is related to the electrolyte conductivity for the calculation
of the surface zeta potential, the streaming current is related to the
cell constant (the calculation of the zeta potential from streaming
current / streaming potential measurement is explained in chapter
4.1).
Since the electrical conductivity is independent of the geometry of

the capillary, the streaming potential is not affected by the dimen-
sions of the streaming channel 2. On the other hand the streaming
2
The streaming potential is suppressed by surface conductivity, even at reasonable
ionic strength, if the channel height goes below 30 µm (Werner et al., 1998) and by
undeveloped flow conditions if the channel height exceeds 200 µm (Yaroshchuk et al.,
2013).
22
current changes with the capillary size, especially with the dimen-
sion determining the flow, i.e. the channel height in the case of a
slit channel between planar material surfaces.
For a reliable and reproducible evaluation of the surface zeta poten-
tial, the measuring conditions have thus to comply with certain
requirements. The streaming potential and streaming current,
respectively, depend on the volume flow rate of the aqueous
solution. Therefore relative changes of these parameters are used
(for the zeta potential calculation the volume flow rate is replaced
by the differential pressure – refer to the calculation of zeta poten-
tial in chapter 4.1).
The easiest approach is to measure the streaming potential (U str) or

streaming current (I str) at fixed volume flow rate (and thus constant
pressure difference Δp) and to correlate the ratio U str /Δp or I str /Δp
with the zeta potential. This approach requires highly reversible
electrodes and is applicable to high streaming potential and stream-
ing current readings at low ionic strength only. A deviation of the
voltage or current reading at zero pressure difference caused by
an asymmetric electrode potential or by electrode polarization will
introduce a severe measuring error.
A more reliable approach is the measurement of streaming potential

and streaming current at various pressure differences. The theory
of streaming potential and streaming current analysis predicts
a linear dependence of these electrical signals on the pressure
difference. The measurement of streaming potential or current at
a minimum of two distinct pressure differences is thus required to
calculate the corresponding difference quotient.
A better measuring statistic is obtained by recording the streaming

potential or streaming current continuously with increasing volume
flow rate and thus increasing pressure difference (pressure ramp).
Figure 4.2 compares the different approaches and indicates the
possible error of the measurement at a single constant pressure.
23
Fig. 4.2.
Comparison of
constant pressure
and pressure ramp
modes for stream-
ing potential analysis.
The deviation in the
slope (here: 7.4 %)
scales with offset
(electrode asym-
metry).
The effect of ionic strength on the reproducibility of the stream-

ing potential and streaming current measurements is eliminated
by supplying an aqueous solution with known ionic strength. For
reasons discussed in chapter 6.2 the use of an aqueous solution of
a 1:1 electrolyte (such as NaCl, KCl or KNO 3) at an ionic strength
of 0.001 mol/l is commonly accepted. 3
The streaming potential and streaming current measurements are

performed in two different modes, which are determined by the
shape of the solid sample:
Tangential mode for flat samples
For solids with a flat surface the tangential mode is commonly

applied 4. Two samples are mounted opposite each other with the
planar surfaces facing the streaming channel, i.e. a slit capillary
3
The use of a solution containing chloride is preferable to KNO 3 to guarantee a better
performance of the commonly used Ag/AgCl electrodes.
4
Materials with significant porosity offer the possibility for both tangential and
permeation modes of streaming potential and streaming current measurements.
24
of rectangular shape 5. The aqueous solution passes through this

channel tangentially to the solid surfaces.
Permeation mode for samples of irregular shape
Fibers and granular media are mounted in a randomly arranged

plug. The plug has to offer sufficient permeability for the liquid flow
but also enough flow resistance to obtain a reasonable pressure
difference. The aqueous solution passes through the capillary net-
work of the fiber or particle plug. The permeation mode is also
applicable to rigid material such as a porous filter, fabric or ceramic
sample.
Figure 4.3 illustrates the different methods for streaming potential

and streaming current measurements. The consequences of the
selected measuring mode on the zeta potential calculation are
discussed in chapter 4.1.
Fig. 4.3.
Tangential streaming
potential and stream-
ing current (left) and
permeation mode
(right) for the analysis
of the solid surface
zeta potential.
The needs for a stationary solid sample and the formation of an

appropriate capillary or capillary system restricts the range of
application of the streaming potential and streaming current tech-
nique to macroscopic solid materials. On the other hand, particles
in dispersions or emulsions represent systems which are character
ized by their electrophoretic mobility or electroacoustic effects for
the evaluation of the zeta potential.
5
For samples with irregular size or disks a rectangular channel is approximated.
25
For surface charge characterization of particles the methods of

streaming potential/streaming current and electrophoretic mobility 6
approach each other, although an overlapping of applications has
not been reported yet. While the measurement of electrophoretic
mobility using dynamic light scattering commonly fails above a
particle size of 1 µm, the lower limit of particle size suitable for
streaming potential analysis depends on the design of the analytical
instrument. Skartsila and Spanos (2006) have reported zeta poten-
tial for hydroxyapatite with particle size as small as 8 µm using the
streaming potential method.
ζ When moving an aqueous solution relatively to a solid

sample, an electrical response – the streaming potential
or the streaming current – is generated.
The aqueous solution can stream across a planar sur-

face (tangential mode) or through a porous sample
(permeation mode).
In modern instrumentation the streaming potential and

streaming current are continuously monitored with
increasing pressure difference.
6
The applicability of electroacoustic methods is limited to ceramics and mineral par-
ticles since it is necessary to maintain a significant difference in their density with
respect to the aqueous solution.
26
 4.1. Zeta potential calculation
The fundamental equations that relate the electrokinetic phenomena

of the streaming potential and the streaming current to the zeta
potential have been derived by Hermann von Helmholtz and Marjan
von Smoluchowski (cf. chapter 2).
Helmholtz-Smoluchowski equations
For solid materials with a planar surface the application of Eq. 4.1
for the zeta potential calculation is most accurate. For a derivation
of this equation refer, for example, to Werner et al., 1998.
Eq. 4.1
Here the measured streaming current coefficient dI str /dΔp is related

to the cell constant L/A of the streaming channel (the gap between
adjacent solid samples). L is the length of the rectangular slit
channel formed between two planar surfaces and A is its cross-
section, A = W x H, with channel width W and gap height H. Figure
4.4 shows a schematic representation of the arrangement of solids
with planar surfaces indicating the dimensions of the streaming
channel. η and ε x ε 0 are the viscosity and dielectric coefficient of
the electrolyte solution. For dilute aqueous solutions the viscosity
and dielectric coefficient of water are used.
Fig. 4.4.
Schematic repre-
sentation of the
rectangular slit
channel between
adjacent solid
samples with a
planar surface. L, W
and H are the length,
width and height of
the streaming
channel.
27
The streaming current in Eq. 4.1 can be substituted by the stream-

ing potential using Ohm’s law, I str = U str /R, where R is the electrical
resistance inside the streaming channel. The zeta potential is then
expressed as
Eq. 4.2
In the following discussion, Eq. 4.1 and Eq. 4.2 are referred to
as the evaluation approach by Helmholtz and Smoluchowski (HS
approach).
The application of the HS equations requires exact knowledge

about the geometry of the streaming channel, i.e., the cell con-
stant L/A. For the rectangular slit the length L and width W are
determined by the solid sample size. The gap height H is calculated
from the measured volume flow rate of liquid passing through the
streaming channel and the generated differential pressure.
In practice the zeta potential of planar samples of known geometry

should only be calculated from streaming current data according to
Eq. 4.1 due to the following reasons:
• Eq. 4.1 requires only one measured parameter (dI str /dΔp)
instead of two (dU str /dΔp, R), which reduces the measuring
error.
• In case of samples with conducting edges, the measurement
of the cell resistance R is affected, which disables the use of
Eq. 4.2.
The HS equations are well established for zeta potential investi-

gations of planar solids, but is not suitable for the zeta potential
evaluation of all irregularly shaped samples.
28
Helmholtz-Smoluchowski approximation
For sample types where the cell constant L/A of the streaming
channel is unknown (like planar solids of irregular size, fibers,
textiles and granular samples) a derivative of the Helmholtz-
Smoluchowski equations is applicable.
By using the definition of electrical conductivity κ,
Eq. 4.3
Eq. 4.2 is replaced by
Eq. 4.4
or, in terms of streaming current, by using Ohm’s law
Eq. 4.5
Since the electrical conductivity κ inside the streaming channel

cannot be measured directly, it is commonly replaced by the con-
ductivity of the bulk electrolyte solution κ B. This is a valid approach
for non-conducting samples.
However, if the solid sample contributes to the conductance

inside the streaming channel, the zeta potential gets rated too
low. This is due to the fact that the streaming potential, though
it “experiences” an increased conductivity (from electrolyte and
sample) inside the streaming channel, is only related to the smaller
(electrolyte) conductivity. The zeta potential calculated according
29
to Eq. 4.4 is therefore rated too low and denoted as the “appar-
ent” zeta potential.
In order to obtain the correct or “real” zeta potential, Fairbrother and

Mastin (1924) simply determined the cell constant L/A according
to Eq. 4.3 by measuring the electrolyte conductivity κhigh and resis-
tance inside the streaming channel R high at high ionic strength.
Eq. 4.6
Their approach assumes that the additional conductance intro-

duced by the solid sample is suppressed when the conductivity
of the electrolyte solution increases. It is primarily applicable to
correct for the influence of surface or interfacial conductance.
For other sources of conductance, i.e., electronic or ionic con

ductance of the solid sample, the assumption of suppressing this
additional conductance at high ionic strength may be invalid.
The Helmholtz-Smoluchowski equation is used to calculate the

zeta potential of flat samples, where the geometry of the streaming
channel, i.e. the cell constant L/A, is exactly known.
For the zeta potential evaluation of all irregularly shaped samples,
where L/A is unknown, an approximation of the HS approach is
applicable.
ζ The Helmholtz-Smoluchowski equation is used to calcu-

late the zeta potential of flat samples, where the geometry
of the streaming channel, i.e. the cell constant L/A, is
exactly known.
For the zeta potential evaluation of all irregularly shaped

samples, where L/A is unknown, an approximation of the
HS approach is applicable.
30
 4.2. Material and interfacial conductance
Different sources of electrical conductance may contribute to the

total conductance inside the streaming channel and falsify the zeta
potential determined by streaming potential measurements.
Surface conductance
Common to all solid-liquid interfaces is the occurrence of the so-

called surface or interfacial conductance. It arises from the accu-
mulation of a cloud of ions in the vicinity of the solid surface that
compensates the surface charge (according to the model of the
electrochemical double layer shown in Figure 3.1). The ion con-
centration at the solid-liquid interface is then increased compared
to their concentration in the bulk liquid phase, giving rise to the
increased conductivity in the interfacial liquid “layer”.
The effect of surface conductance on the zeta potential can be

assessed experimentally by measuring streaming potential and
streaming current at low ionic strength. Figure 4.5 shows the
dependence of a glass surface’s zeta potential on the concentration
or ionic strength of an aqueous solution of a 1:1 electrolyte.
Fig. 4.5.
Zeta potential of a
glass surface as a
function of the ionic
strength of a 1:1
electrolyte. Zeta
potential data evalu-
ated from Eq. 4.1
(correct) and Eq. 4.4
(apparent) are com-
pared.
31
The zeta potential was calculated according to Eq. 4.1 (correct)

and Eq. 4.4 (apparent), respectively. At low ionic strength a signifi-
cant deviation between the correct and the apparent zeta potential
arises, which diminishes at an ionic strength of 5×10 -4 mol/l.
The difference in the zeta potential data at low ionic strength is

explained by the surface conductance. At higher ionic strength
(increased electrolyte conductivity) the effect of sample surface
conductance is suppressed 7.
For an insulating and non-porous solid material the zeta potential

data calculated from Eq. 4.1 and Eq. 4.4 coincide at a sufficiently
high ionic strength (for solids with a planar surface, the threshold
concentration is 0.001 mol/l).
Intrinsic material conductance
Various solid materials exhibit an “intrinsic” conductance that is

significantly higher than the surface conductance 8. In these cases
a deviation between the correct and the apparent zeta potential
may still occur, even at an ionic strength that suppresses the effect
of surface conductance (as shown in Figure 4.6).
For a metal surface the contribution of the electrical conductance

to the total conductance inside the streaming channel is obvious.
The enormous effect on the apparent zeta potential renders the use
of Eq. 4.4 inapplicable. A semiconductor shows smaller electrical
conductivity than a metal and the difference between the correct
and apparent zeta potential is reduced.
7
Note that the effect of surface conductance depends on both the ionic strength
of the electrolyte solution and the distance between adjacent solid surfaces. In the
given example the distance between glass slides was 100 µm. For smaller distances
between solids, e.g. in fiber plugs or powder beds, a higher ionic strength is required
to suppress the effect of surface conductance.
8
Surface conductance occurs in the range of 1-2 nS (depending on the solid material
and the ionic strength of the electrolyte solution).
32
Ionic conductance arises for insulating yet porous materials when

they get soaked in an aqueous electrolyte solution. The same is
true for a thin film surface coating that shows swelling in water. In
both cases ions enter the porous or swollen sample surface layers,
resulting in an increased conductance. The presence of ionic con-
ductance has an effect on the apparent zeta potential similar to that
of a semiconductor surface. Different from electrical cond uctance,
ionic conductance strongly depends on the ionic strength of the
electrolyte solution and – in case of swelling – also depends on the
electrolyte pH.
A comparison of the zeta potential data evaluated by Eq. 4.1 and

Eq. 4.4 helps to elucidate the behavior of such complex solid
materials in an aqueous solution.
Fig. 4.6.
Comparison of zeta
potential data evalu-
ated from Eq. 4.1
(correct) and Eq.
4.4 (apparent) for
insulator, metal,
semiconductor,
membrane (porous
material) and protein
layer (swelling).
33
ζ If the solid sample contributes to the conductance inside

the streaming channel, the streaming potential measure-
ment leads to a zeta potential, which is rated too low. The
difference between this so-called “apparent” zeta poten-
tial and the correct zeta potential may be affected by:
• Surface conductance, which is common to all solid-

liquid interfaces. Its influence can be suppressed at
higher ionic strength.
• Electrical conductance, which cannot be suppressed.
• Ionic conductance, which is observed for porous or

swollen surfaces. Its effect on zeta potential determi-
nation is dependent on ionic strength as well as the
electrolyte pH (in case of swelling).
34
Instrumentation
5. Instrumentation
Prior to the introduction of the first commercial instrument for
streaming potential measurement in 1990, the lack of such an
analyzer caused many academic researchers to build their own
apparatus (Schausberger and Schurz, 1979; Van den Hoven and
Bijsterbosch, 1987; Scales et al., 1992; Nyström et al., 1989;
Zembala and Dejardin, 1994; Möckel et al., 1998). Although the
ingredients to generate and measure the streaming potential have
little complexity, the development of an instrument for a reliable
surface zeta potential analysis requires high-end electronics, high-
precision sample holders and measuring cells, and a deep under-
standing of various influences on the quality of the measured data.
The minimum configuration of a streaming potential apparatus

requires a measuring cell with an appropriate sample holder for the
solid materials under investigation, electrodes for the streaming
potential measurement (dc voltage) and a corresponding voltmeter,
as well as a container with measuring liquid which is connected
to the measuring cell. Figure 5.1 schematically shows the setup
of such minimum configuration of a streaming potential analyzer.
The whole setup must be protected from external electromagnetic
fields by putting it in a grounded metal cage. Here, in addition
to the streaming potential, the electric conductivity and pH of the
aqueous solution must be measured separately.
A hydrostatic pressure difference is induced manually by lifting the

liquid container.
Fig. 5.1.
Schematic view
of the minimum
setup for streaming
potential measure
ment (adapted
from Zembala and
Adamczyk, 2000).
1 measuring cell
2 electrodes
3 voltmeter
4 conductivity probe
35
Instrumentation
A more operator-friendly setup for streaming potential measure-

ment has an integrated driving force for the measuring solution,
e.g. a connection to a pressurized nitrogen tank (Van den Hoven
and Bijsterbosch, 1987) or a piston pump (Schausberger and
Schurz, 1979), and pressure transducers connected to a mano
meter. Adding the pH and conductivity measurement to the stream-
ing potential apparatus completes the zeta potential analysis even
further (Scales et al., 1992).
Fig. 5.2.
Schematic view of
an operator-friendly
setup for streaming
potential measure-
ment (adapted from
Scales et al., 1992).
1 measuring cell
2 electrodes
3 voltmeter
4 pressure transducer
5 pH electrode
6 conductivity probe
7 two-way solenoid
valve
The first commercially available streaming potential analyzer

introduced by Anton Paar GmbH, Austria, in 1990 (EKA Electro
Kinetic Analyzer, Figure 5.3) was based on a prototype developed
by Jacobasch and co-workers (Jacobasch et al., 1986; Schurz et
al., 1986; Jacobasch, 1989). The EKA introduced a fully auto-
mated analysis of the zeta potential and its pH dependence by
offering a combination with a titration unit. It further allowed for the
zeta potential analysis of various types of solid materials such as
planar samples, fibers and granular media by providing a variety of
different measuring cells and sample holders. What is more, the
EKA integrated the measurement of the electrical resistance inside
the measuring capillary (either the rectangular channel between
planar surfaces or the capillary network within a fiber or powder
plug). This cell resistance helps compensate surface conductivity
36
Instrumentation
according to Eq. 4.6 and detect air entrapped inside the measuring
cell (cf. chapter 9.1).
Fig. 5.3.
Components of the
EKA Electro Kinetic
Analyzer (A48IB08-D,
2003).
A electrolyte reservoir
B, C pinch solenoid
valves
D temperature sensor
E rotating pump
F differential pressure
transducer
G electrodes
H measuring cell
J sample
Almost at the same time another streaming potential analyzer

was introduced based on a concept of Thomas and co-workers
(Pogrovsky et al., 1999).
Solid surface zeta potential analysis using the streaming poten-

tial method was complemented by the measurement of streaming
current (Werner et al., 1998). The streaming current opened the
path to a more accurate analysis of the zeta potential for materials
with a complex surface (Zimmermann et al., 2013).
The accumulated knowledge in solid surface zeta potential analysis

was implemented in the most recent commercial instrument
for streaming potential and streaming current measurement
(SurPASS, Anton Paar GmbH, Austria). In order to calculate the
zeta potential correctly according to Eq. 4.1, information about the
volume flow rate of the aqueous solution is required. The SurPASS
37
Instrumentation
instrument determines the flow rate. A diagram of this instrument

is shown in Figure 5.4.
Fig. 5.4.
Components of the
SurPASS electro
kinetic analyzer
(A48IB046en-B, 2013)
A 3-way valve,
B syringes for
electrolyte transport,
C pressure trans
ducers, electrodes,
D measuring cell,
E pH electrode,
F conductivity probe

 5.1. Measuring cells
The development of appropriate measuring cells for mounting

specific solid samples followed the requirements of evolving appli-
cations for solid surface zeta potential analysis.
The first analyses of the zeta potential for macroscopic solids con-
sidered fibrous material such as cellulose fibers (Fairbrother and
Mastin, 1924; Biefer and Mason, 1954; Onabe, 1978), polymer
fibers and glass fibers. Examples of measuring cells for fiber
samples are shown in Figure 5.5.
38
Instrumentation
Fig. 5.5.
Measuring cells for
the streaming poten-
tial measurement of
fibrous material.
(a) EKA Electro

Kinetic Analyzer
(Börner et al., 1994).
(b) SurPASS electro

kinetic analyzer
(A48IB046en-B,
2013).
The application of the measuring cell for fiber samples may be

extended to the analysis of granular media (Fuerstenau, 1956;
Skartsila and Spanos, 2006) by using a filter support. Figure 5.6
illustrates a setup for the zeta potential analysis of a powder
sample (the particle size is determined by the mesh of the support
filter and the applicable pressure and flow rate).
Fig. 5.6.
Schematics of a
sample holder for
granular powder
(A48IB08-D, 2003).
39
Instrumentation
The need soon arose for a zeta potential analysis of materials with
a flat surface such as glass plates (Van Wagenen and Andrade,
1980; Norde and Rouwendal, 1990; Scales et al., 1992) or polymer
films (Jacobasch and Börner, 1983). The concept of the stream-
ing potential method, i.e. passing an aqueous solution through
an appropriate capillary, was translated to flat surfaces by several
researchers. Figure 5.7 shows examples of measuring cells for
solid plates and films of large size.
Fig. 5.7.
Measuring cells
for zeta poten-
tial analysis of
flat surfaces of
(a) microscope
slides, 76 mm x 26
mm (Van Wagenen
and Andrade, 1980),
(b) polymer films,

127 mm x 50 mm
(A48IB08-D, 2003),
and
(c) rigid samples,
55 mm x 25 mm
(A48IB046en-B,
2013).
The demand for zeta potential analysis of a flat sample with a

smaller size triggered the development of a differently designed
measuring cell (Werner et al., 1998). This cell type offers the
additional benefit of a continuous variation of the distance between
adjacent sample surfaces, allowing an in-depth analysis of con
ductance effects at the solid-liquid interface (Werner et al., 2001).
Figure 5.8 shows the schematics of an adjustable gap cell.
40
Instrumentation
Fig. 5.8.
Schematc drawing
of an adjustable
gap cell for the zeta
potential analysis of
small samples with
a planar surface
(Yaroshchuk and
Luxbacher, 2010)
This series of measuring cells for fibers, granular media, large

and small samples with a planar surface covers the majority, but
certainly not all material samples of interest. Small disks, the inner
surface characterization of capillaries such as hollow fiber mem-
branes, ceramic filter modules, or strongly swelling samples
(leather, hydrogel) require proprietary solutions for sample holders.
ζ An instrument for reliable surface zeta potential analysis

requires high-end electronics, high-precision measuring
cells and a pulsation free liquid circuit, as well as a deep
understanding of various influences on the quality of the
measured data.
The most recent commercial instruments for streaming

potential / streaming current measurement increase the
reliability of surface zeta potential analysis and its accep-
tance as a valuable measuring technique for solid surface
characterization.
41
Dependences of the zeta potential
6. Dependences of the
zeta potential
The zeta potential at the solid-liquid interface is affected by a num-
ber of different properties of both the solid material and the liquid
phase. These properties are summarized in Table 6.1 and their
effect on the zeta potential and conclusions drawn from its de
pendences are discussed in turn.
Table 6.1.
Solid, liquid, and Liquid properties Solid properties Other
interfacial properties
affecting the zeta pH value Size Measuring time
potential at the solid-
liquid interface
Ionic strength Porosity Temperature
Additive Electronic Material

concentration conductance swelling
Surface roughness
 6.1. pH value
The charge formation at the solid-liquid interface is driven by

different processes (see chapter 3.1) among which the acid-base
reaction between surface functional groups and water and the
physical adsorption of water ions are the dominant mechanisms.
Since both processes strongly depend on the pH of the aqueous
solution, pH is the most important parameter of the liquid phase
that affects the zeta potential.
When reporting zeta potential data it is therefore necessary to refer

to the pH of the aqueous solution used for the zeta potential
analysis. The pH dependence of the zeta potential is furthermore
the most studied dependence of the zeta potential. A primary
purpose of a pH titration of the solid-liquid interface is the
42
assessment of the isoelectric point (IEP). Figure 6.1 shows the pH

dependences of the zeta potential for solid surfaces with acidic,
basic, and amphoteric functionalities. At a certain pH the zeta
potential assumes 0 mV and reverses its sign, respectively, when
moving from high to low pH and vice versa. The pH of the aqueous
solution at which the zeta potential reverses its sign is known as
the IEP. In other words, the IEP is the pH of the aqueous solution
where the net electrokinetic charge density becomes 0 C/m 2. The
assumption that the surface charge disappears at the IEP is not
correct. It is advisable to assume an equilibrium between negatively
and positively charged surface groups, which in average give zero
net charge.
Fig. 6.1.
pH dependences of
the zeta potential
for material surfaces
with acidic, basic,
and amphoteric
behavior (Nygård et
al., 2002; Böhme et
al., 2001)
The IEP is a strong indicator for the chemistry of the functional

groups that are present on the solid surface. For material surfaces
which feature a single type of functional surface group, the IEP
is related to the acidic or basic strength of this group and thus to
its pK value. This is an accurate method to calculate the pK value,
which takes into account the plateau value of the zeta potential
at a pH where acidic surface groups get completely dissociated
or basic surface groups get completely protonated (Jacobasch,
1989). The pK value is then calculated according to
43
Eq. 6.1
where pH(½ζ plateau) is the pH at which the zeta potential assumes

half the magnitude of its plateau value ζ plateau, F is Faraday’s constant
(96485 C/mol), R is the molar gas constant (8.314 J/mol/K) and T
is the absolute temperature.
In Figure 6.1 the plateau values of the zeta potential are nicely
obtained for material surfaces with acidic, basic and amphoteric
character that feature a single type of surface functional group. The
isoelectric points and the corresponding pK values for these sur-
faces are summarized in Table 6.2.
The pK values of acidic (basic) surface functional groups are

commonly higher (lower) than the pK values of the corresponding
acid (base) in solution. The main reason for this observation is the
close proximity of surface functional groups that affects the
dissociation (protonation) equilibrium. Charged surface groups
prevent the dissociation (protonation) of neighboring groups by
electrostatic repulsion.
Table 6.2.
Isoelectric points, Surface behavior IEP ζ plateau / mV pK
plateau values of the
zeta potential and pK
Acidic 2.8 -57 2.7
values obtained from
the pH dependence
of the zeta potential Amphoteric 7.0 -34 7.4
shown in Figure 6.1
Basic 8.8 +38 8.6
For the majority of applications, technical samples are used that

show a heterogeneous composition of surface functional groups.
For a material surface with two or more similar or dissimilar types
of functional groups, the occurrence of a pronounced plateau value
44
of zeta potential is rather unlikely. Since Eq. 6.1 is not applicable

if a plateau value of the zeta potential is missing, the IEP is used
instead to describe the acidity or basicity of the material surface. A
comparison of the IEP and the corresponding pK value of the sur-
face functional group in Table 6.2 shows that only a small error is
introduced when equating the IEP and pK value.
Surface functional groups that interact with water in terms of acid-

base reactions introduce a hydrophilic character to the material
surface. The absence of such functional groups renders material
surfaces hydrophobic. But even for hydrophobic surfaces a zeta
potential arises which strongly depends on the pH of the electrolyte
solution.
The charge formation by adsorption of water ions discussed
in chapter 3.1 leads to an equilibrium surface concentration
of adsorbed negative ions (hydroxide ions) and positive ions
(hydronium ions), which is obtained at pH 4. At this pH we gener-
ally find the IEP for hydrophobic surfaces that lack functional sur-
face groups, such as polymers.
Besides the IEP at pH 4 the pH dependence of the zeta potential

reveals the difference in the hydrophobic character of material sur-
faces without acidic, amphoteric or basic functional groups. Figure
6.2 shows the pH dependence of the zeta potential for a series of
technical polymer surfaces with different hydrophobicity. While the
IEP at pH 4 is observed for all polymers, the magnitude in the zeta
potential decreases in the series PTFE > PP > PMMA. The order
of this polymer series at higher pH reflects a decrease in hydro-
phobicity.
45
Fig. 6.2.
pH dependence
of zeta poten-
tial for poly(methyl
methacrylate),
PMMA, low-density
poly(ethylene), LDPE,
and Teflon AF
(Zimmermann
et al., 2001).
Besides the representation of the acidity or basicity of the material

surface, the IEP may be used to indicate specific ion adsorption
on the material surface. The pH dependence of zeta potential is
commonly recorded in a 1:1 electrolyte such as NaCl or KCl of a
certain ionic strength. A 1:1 electrolyte is considered inert with
respect to surface interaction. Inert behavior is demonstrated by an
IEP which remains independent of the ionic strength of the aqueous
electrolyte solution. Figure 6.3a gives experimental evidence for
the absence of a specific adsorption of KCl on a poly(L-glutamic
acid) layer grafted on a fluoropolymer support (Zimmermann et
al., 2006). When using a more complex electrolyte (e.g., a 3:1
electrolyte such as LaCl 3 ), specific adsorption may be expected
which gives rise to a shift of the IEP at higher ionic strength (Figure
6.3b). Certain materials such as collagen even show an affinity to a
1:1 electrolyte (Figure 6.3c).
46
Fig. 6.3.
Evidence for specific
ion adsorption on
the material surface
indicated by a shift
of the IEP at different
ionic strength.
a. No adsorption
of KCl on a poly
(L-glutamic acid)
layer (Zimmermann
et al., 2006).
b. Specific adsorp-
tion of LaCl3 on a
poly(ethylene-alt-
maleic anhydride)
layer (Zimmermann,
private communi
cation).
c. Specific adsorp-
tion of KCl on
collagen
(Freudenberg et al.,
2007).
ζ The pH value is the most important parameter of the liquid

phase that affects the zeta potential and must always be
reported with the corresponding zeta potential data.
The pH dependence of the zeta potential reveals the iso-

electric point (IEP) at the pH where the zeta potential
assumes 0 mV.
Hydrophobic surfaces without functional surface groups

(e.g., polymers) have the same IEP at pH 4.
47
 6.2. Ionic strength
The definition of the zeta potential as the electrical potential at

the plane of shear between the stationary layer and the mobile
layer of the electrochemical double layer (EDL, cf. Chapter 3) at
the solid-liquid interface makes it susceptible to changes in the
ionic strength of the aqueous solution. Irrespective of the material
surface, the magnitude of the zeta potential decreases with
increasing concentration of a 1:1 electrolyte such as NaCl or KCl.
This observation is commonly explained by the compression of the
EDL at high ionic strength. The extension of the EDL is described
by the Debye length κ -1,
Eq. 6.2
where ε 0 is the permittivity of free space, ε r is the dielectric con-

stant of the aqueous solution, k B is the Boltzmann constant, T is
the absolute temperature, N A is the Avogadro number, e is the
elementary charge and I is the ionic strength.
Figure 6.4 compares the dependence of the zeta potential on the

ionic strength of an aqueous KCl solution for a glass surface with
the compression of the electrochemical double layer (decay of the
Debye length) with increasing electrolyte concentration.
Fig. 6.4.
Dependence of zeta
potential for glass
on the ionic strength
of an aqueous KCl
solution. Comparison
with decay of Debye
length, indicating
the extension of the
electrochemical
double layer.
48
The change in the zeta potential with increasing ionic strength

deviates from a regular decrease in magnitude when exchanging
the 1:1 electrolyte by a complex solute (1:2, 2:1, or 3:1 electrolytes
such as Na 2 SO 4 , CaCl 2 , or Al(NO 3 ) 3 , respectively). A deviation is
readily explained by the specific adsorption of divalent or trivalent
ions on the solid surface.
For instance, the complexation of calcium ions, Ca 2+, by carboxylic

acid surface groups diminishes the negative charge, thus render-
ing the surface neutral or even positively charged at high ionic
strength of the calcium compound in solution. When looking at
the intera ction of solid surfaces with complex ions in solution, the
effect of the electrolyte pH on the type of dissolved ions requires
attention. Especially for metal ions such as Al 3+ or Fe 2+, a series of
hydroxo complexes exist at medium and high pH. Ion complexation
in solution not only changes the overall charge but also influences
the interaction with solid surfaces.
The applicability of the streaming potential and streaming current

method is limited by the ionic strength. The lower and upper limits
depend on the quality of the electrodes used to detect the dc
voltage or dc current, and on the quality of the electronic circuit
employed to measure these quantities. The recommended ionic
strength for solid surface zeta potential analysis is 0.001 mol/l.
For an estimation of the surface potential, i.e., the potential

difference at the solid surface, the dependence of the zeta poten-
tial on the ionic strength of the aqueous solution may be employed.
The extrapolation of the zeta potential to infinitely dilute solution
indicates the magnitude of the surface potential.
Other applications require information on the zeta potential at

high ionic strength. For a state-of-the-art streaming potential
analyzer the upper limit of ionic strength is specified at 0.1 mol/l.
Applications such as the characterization of membranes for sea-
water desalination or the study of biomaterials at physiological
buffer conditions require a solute concentration in water that
49
exceeds this upper measuring limit. The extrapolation of the zeta

potential to higher ionic strength enables the evaluation of its sign
and magnitude under real-life conditions.
Adsorption of multivalent ions
The dependence of the zeta potential on the ionic strength of an

aqueous solution with an electrolyte other than NaCl or KCl may
deviate from the general trend shown in Figure 6.4. Choosing HCl
or KOH instead of KCl, we can demonstrate the effect of their
obvious interaction with the solid surface on the zeta potential,
still without increasing the complexity of the electrolyte. Figure 6.5
compares the corresponding concentration dependence of zeta
potential for Teflon ® (Zimmermann et al., 2001). For KCl we identify
the already known steady decrease of the negative zeta potential.
For HCl we find a conversion of the surface charge at a concen-
tration of 10 -4 mol/l (corresponding to the isoelectric point, IEP,
of Teflon ® at pH 4). Increasing the concentration of KOH again
has a different effect. The negative zeta potential first increases,
then passes through a maximum, and finally approaches the value
obtained in the presence of KCl at high ionic strength.
It is obvious that the addition of acid (HCl) or base (KOH) alters the
pH of the aqueous solution and thus the charging behavior of the
solid surface. This specific interaction is reflected by the deviation
of the concentration dependence of zeta potential from that in the
inert electrolyte KCl.
Fig. 6.5.
Dependence of zeta
potential for Teflon®
on the concentration
of KCl, HCl, and
KOH (Zimmermann
et al., 2001).
50
Specific interaction between the solid surface and complex ions

that do not show an effect on the pH of the aqueous solution is
again revealed by a comparison of its concentration dependence of
the zeta potential with that of a 1:1 electrolyte. The pH depen-
dence of the zeta potential at different electrolyte concentration
offers another possibility to distinguish between inert and
specifically adsorbing ions. Figure 6.6 shows the effect of a specific
interaction of calcium ions (Ca 2+) with collagen (Freudenberg et al.,
2007). In Figure 6.6, the zeta potential is represented by the
streaming current coefficient dI str /dΔp. Ca 2+ ions adsorb or bind
specifically and “become part of the solid surface”, thus shifting
the IEP of the pristine collagen surface to a higher pH.
Fig. 6.6.
pH dependence of
streaming current for
collagen at different
CaCl2 concentration
(Freudenberg et
al., 2007). Pristine
collagen is repre-
sented by the stream-
ing current measured
in 1 mmol/l KCl.
51
ζ The zeta potential decreases with increasing ionic

strength due to a compression of the electrochemical
double layer at high ionic strength.
The applicability of the streaming potential and stream-

ing current method is limited by the ionic strength. The
recommended ionic strength for solid surface zeta poten-
tial analysis is 0.001 mol/l.
Specific interaction of complex solutes with solid

surfaces is indicated by (a) a deviation of the dependence
of zeta potential on the ionic strength from the prediction
of the EDL model and (b) by a concentration-dependent
shift of the isoelectric point.
 6.3. Additive concentration
The step from the dependences of the zeta potential on the

electrolyte pH and ionic strength towards its dependence on the
concentration of an even more complex additive is straightfoward.
With the possibility to observe the interaction between solid sur-
faces and adsorbates in solution, we move from solid surface
analysis towards the characterization of liquid-on-solid surface
adsorption processes.
The simplest phenomenon, though not yet fully understood, is the

adsorption of water ions (hydroxide, OH – , and hydronium, H 3 O + )
on hydrophobic surfaces which determines their interfacial charge.
This adsorption process occurs almost instantaneously and is thus
only measurable under steady-state conditions.
The adsorption of divalent or trivalent cations and anions was

discussed in chapter 6.2 and is primarily observed with increas-
ing ionic strength of the corresponding solute. A comparison
with the dependence of the zeta potential on the ionic strength
of a 1:1 electrolyte is required to quantify the effect of selective
52
ion adsorption. The equilibration time for such adsorption pro-

cesses depends on the solid material. In average the adsorption is
complete within seconds, thus again limiting the measurement to
steady-state conditions.
Complex adsorbates are mainly comprised of surfactants and

polyelectrolytes (technical polyelectrolytes, proteins, polypep-
tides, polysaccharides, enzymes). The time for equilibration of the
adsorption of such an adsorbate from dilute solution onto the solid
surface may range from a few seconds to tens of minutes.
As for multivalent cations and anions, the condition of the adsorbate

strongly depends on the electrolyte pH. The ionic strength of the
aqueous solution may also become a driving force for the adsorp-
tion process. Last, but not least, the adsorbate concentration itself
has a critical effect on the adsorption behavior, e.g. surfactants
create micelles at higher concentration (critical micelle concen
tration, cmc), which itself is material-dependent.
The streaming potential and streaming current method is suitable

for the analysis of liquid-on-solid surface adsorption processes
because of the sensitivity of the zeta potential to the outermost
solid surface. In the presence of an aqueous solution of a 1:1
electrolyte for solid surface characterization, the zeta potential indi-
cates the presence of surface functional groups. These surface-
terminated groups interact with the surrounding aqueous solution
and become accessible by the streaming potential and stream-
ing current measurement. Upon liquid-on-solid surface adsorption,
adsorbate molecules get deposited on the solid surface and form
the (new) boundary of the solid-liquid interface. The opposite pro-
cess of adsorption, the desorption of molecules weakly attached to
the solid surface, also results in a change in the surface chemistry,
in the surface charge, and thus in the zeta potential.
The possible contributions to the zeta potential analysis during

adsorption and desorption processes are illustrated in Figure 6.7.
53
Fig. 6.7.
The zeta poten-
tial detects surface
functional groups
(left) and changes
during adsorp-
tion (center) and
desorption (right)
processes.
ζ The streaming potential and streaming current method

can be used for the analysis of liquid-on-solid surface
adsorption and desorption processes. This is possible
due to the sensitivity of the zeta potential to the outermost
solid surface.
 6.4. Size
The sample size decides about the analytical method used for the
zeta potential analysis.
Macroscopic solids of different size and shape are characterized

by the streaming potential and the streaming current measure-
ment while particles in liquid dispersion are analyzed using electro
phoretic mobility or electroacoustic methods. While particles in
dispersion represent a uniform sample which is easily accomodated
in a sample holder of different volume, macroscopic solids require
appropriate measuring cells for zeta potential analysis.
In general the zeta potential is independent of the sample size.

This statement is true in general, provided that the solid material
54
does not introduce an additional complexity such as porosity, con-

ductance, or swelling.
Let us consider a solid material, which may be manufactured in

different shapes such as polypropylene. We may compare the zeta
potential of a polypropylene film with that of the corresponding
fibers and granules. Provided that the polypropylene chemistry is
identical for the film, fiber, and granular surfaces, the zeta poten-
tial is expected to be identical (despite the different approaches
of the tangential streaming potential measurement for the polymer
film and the permeation mode for the fiber plug and the granular
powder). Furthermore, if we disperse polypropylene particles
of < 1 µm size in an aqueous solution of the same composition
(pH, ionic strength) used for the streaming potential analysis and
measure the electrophoretic mobility, the thereby determined zeta
potential resembles the solid surface zeta potential.
Figure 6.8 compares the zeta potential for a glass plate with that of
glass particles. Both the evolution of the zeta potential with the
electrolyte pH as well as the isoelectric point become indistinguish-
able.
Fig. 6.8.
pH dependence
of the zeta poten-
tial for a glass plate
(determined from
tangential stream-
ing current measure
ment) with that
of glass particles
(determined from
streaming potential
measurement in per-
meation mode).
ζ The zeta potential is independent of the sample size,

irrespective of the measuring technique used.
55
 6.5. Porosity
If the bulk material shows a significant porosity, an effect on

the surface zeta potential is to be expected. The term porosity
is understood differently by people working in different research
areas. We distinguish between “macroscopic” porosity, which
enables a visible hydrodynamic flow of liquid at a reasonable flow
rate, and “microscopic” porosity, which disables any liquid flow,
at least in the pressure range up to 1 bar. These two categories of
porosity have different effects on the zeta potential.
Porous coatings on a rigid support introduce ionic conductance

after exposure of the material surface to an aqueous solution. This
conductance may become significant and lead to an apparent
zeta potential calculated from streaming potential measurements
(Eq. 4.4 in chapter 4.1), which is rated too low. The zeta poten-
tial calculated from streaming current measurements (Eq. 4.1 in
chapter 4.1) is not affected by the porosity of surface coatings.
Bulk material porosity again introduces ionic conductance carried

by water and electrolyte ions that enter the porous structure. The
effect increases with the porosity and thickness of the material
sample. Again the apparent zeta potential is significantly affected.
Bulk “macroscopic” porosity also affects the streaming current
measurement and thus the zeta potential calculated according to
Eq. 4.1.
The magnitude of the effect and the consequences derived there-

from are discussed below for a series of microfiltration mem-
branes with different pore sizes.
In the tangential measurement of streaming current a differential

pressure is applied between both ends of a streaming channel
formed between two membrane samples. The total streaming
current I tot
str measured in this configuration is composed of the
C
“external” streaming current in the channel, I str , and an “internal”
streaming current in the pores of the membrane or membrane
56
P
support, I str . The classical Helmholtz-Smoluchowski approach
(Eq. 4.1) predicts a linear dependence of the “external” streaming
current on the gap height of the streaming channel, i.e. the dis-
tance between membrane surfaces. The slope of this linear relation
is a function of the zeta potential of the membrane surface, ζ external.
For membranes we have to add a constant term to the Helmholtz-
Smoluchowski equation that represents the streaming current
inside pores according to (Yaroshchuk and Luxbacher, 2010)
Eq. 6.3
where εε 0 and η are the dielectric constant and viscosity of water,

W and L are the width and length of the streaming channel, H C and
H M are the gap height of the streaming channel and the membrane
thickness, γ is the porosity of the membrane or membrane support,
and ζ internal is the effective zeta potential of the inner pore surface. A
similar equation is derived for the electrical conductance inside the
measuring cell, C tot, where (bulk) electrolyte conductivity, κ B, and
conductivity inside pores, κ M, contribute according to
Eq. 6.4
Determining the contributions of the streaming current inside the

porous membrane structure and of the membrane body con
ductance requires the measurement of streaming current, electrical
conductance, and volume flow rate at different gap heights of the
streaming channel.
Figure 6.9 compares the streaming current coefficient dl tot

str / d∆p
meas ured at different gap heights H C for mixed cellulose micro
filtration membranes (MF membranes) with different nominal pore
sizes.
57
While the contribution of streaming current inside pores and mem-

brane body conductance is almost negligible for the MF membrane
with 0.025 µm pore size, their effects are significant at 0.1 µm pore
size and become considerable at 5.0 µm pore size.
The dependences of both the streaming current and the con

ductance on the channel gap height is strictly linear, with R2 > 0.99.
This linearity and the reasonable number of data points (possible
adjustment of different gap heights obeying laminar flow con
ditions) enable the accurate determination of the slope (i.e. the
zeta potential of the membrane surface) and an extrapolation of the
offset value.
Fig. 6.9.
Dependences of
streaming current
coefficient dl tot
str / d∆p
and electrical con-
ductance Ctot for
mixed cellulose MF
membranes on the
gap height HC of the
streaming channel.
58
Table 6.3.
Zeta potential of mixed cellulose MF membranes calculated from classical Helmholtz-
Smoluchowski equation and streaming potential measurement, and zeta potential
of membrane surface calculated from Eq. 6.3 (average zeta potential and standard
deviation for measurements at min. 5 different gap heights HC ). For MF membranes with
0.025 µm and 0.1 µm pore size, ζSmoluchowski is rated too low, while streaming potential
inside pores of 5.0 µm size contributes to the total zeta potential.
Pore size ζ Smoluchowski ζ external conductance

/ µm / mV / mV inside pores / µS
0.025 –26.6 ± 2.7 –39.8 ± 0.4 0.26
0.1 –24.9 ± 1.6 –32.2 ± 0.4 0.54
5.0 –42.1 ± 1.1 –27.9 ± 1.2 1.53
By taking the streaming current inside the porous membrane

structure into account, the zeta potential is calculated with
improved reproducibility. Table 6.3 compares the zeta potential
calculated from Eq. 4.4 with the correct zeta potential calculated
by Eq. 6.3 for the same type of mixed cellulose MF membranes
with different pore size.
The knowledge of an effective zeta potential of inner pore surfaces

is important for membrane processes where the porous structure
of symmetrical membranes or the porous support of composite
membranes have a significant influence on the filtration process.
ζ The zeta potential calculated from streaming current

measurements is not affected by the porosity of surface
coatings.
Bulk material porosity affects the streaming current

measurement and an extension of the Helmholtz-
Smoluchowski equation is required to calculate the correct
zeta potential.
59
 6.6. Electronic conductance
Intrinsic material conductance has the most considerable effect

on the solid surface zeta potential. Different to the effects of
ionic conductivity introduced by material or surface swelling and
porosity of the bulk sample or a surface coating, electronic con-
ductance occurs independently of the aqueous solution. Examples
of materials with electronic conductance are silicon wafers (semi-
conductors), carbon fibers and coatings (e.g., DLC, diamond-like
Carbon) and, of course, metals. Metals also account for electro-
chemical reactions with water and solutes of the aqueous solution.
Electronic conductance behaves independently of the ionic strength

of the aqueous solution. Therefore it is not possible to suppress
the effect of electronic conductance on the apparent zeta potential
by increasing the solute concentration, as suggested for porous
material, for example. Depending on the nature of the conductive
sample, the effect on the streaming potential may be enormous,
i.e. the streaming potential may approach the detection limit of
the electronics of a streaming potential analyzer. Even for a state-
of-the-art instrument with high-end electronics that allows for the
measurement of extremely small streaming potential signals, the
lack of knowledge of the electronic conductance disables com-
pensation for the additional conductivity when calculating the
zeta potential. Electronic conductance may therefore suppress
the apparent zeta potential value completely, which is why almost
no zeta potential data for metals is reported in relevant literature.
Furthermore, there is a “rumor” that zeta potential analysis is not
possible on metal surfaces.
Unlike the complexity of bulk material porosity described in the

previous chapter, the streaming current is not affected by
electronic conductance and allows for the zeta potential analysis
of metal surfaces. However, the applicability of the streaming
current measurement for metal surface analysis is determined by
the electroc hemical stability of the metal in an aqueous solution.
We distinguish two categories of metals: noble metals with electro
chemically inert behavior in water, and base metals that oxidize/
corrode in an aqueous solution.
60
Recent literature reports on the zeta potential for titanium and

titanium alloys (Roessler et al., 2002; Cai et al., 2006; Jirka et al.,
2013), stainless alloys (Martin Cabanas et al., 2012), diamond-like
Carbon (Jelinek et al., 2010b) and gold (Schrems et al., 2011). For
more information refer to the corresponding sections of chapter 8.
ζ Electronic conductance has a considerable effect on the

apparent zeta potential.
The streaming current measurement is not affected by

electronic conductance and allows for the zeta potential
analysis of metal surfaces. However, this only applies to
metals with electrochemically inert behavior in an aqueous
solution.
 6.7. Surface roughness
As discussed in chapter 6.4 the zeta potential is independent of the

sample size. We obtain the same zeta potential (sign and magni
tude) for different shapes and sizes of a certain material, e.g., films,
fibers or particles. It may be obvious to conclude that the zeta
potential thus behaves independently of surface roughness as well.
However, this conclusion is challenged when considering the well
known phenomenon of the lotus effect. The angle of contact of a
water droplet on a surface increases with roughness in the nano-
meter range. Like the water contact angle, the zeta potential is an
interfacial property of the solid-liquid interface. Although an effect
of surface roughness on electrokinetic phenomena was predicted
by Bikerman (1942) and is discussed for electro-osmotic flow by
Messinger and Squires (2010), there is no evidence yet reported
for the influence of roughness on the zeta potential9.
9
The author is aware of only one paper reporting an apparent effect of surface
roughness on the streaming potential measurement (Schnitzer and Ripperger, 2008).
However, there is strong evidence that the effect described in this paper is due to ionic
conductance in the porous fabrics.
61
Surface roughness and the related surface area certainly require

consideration for the zeta potential analysis of heterogeneous
samples. In case of fibers and powders, the corresponding sample
plugs are in contact with the walls of the sample holder (e.g. a
glass or polymer cylinder), whose contribution becomes negligible
when comparing the surface areas of the smooth cylinder wall and
the rough fiber or particle surfaces. A more important example for
the consideration of surface roughness is the analysis of a flat sur-
face of a rigid material such as a glass slide. A clamping-cell type
of sample holder (Walker et al., 2002) is used to mount the rigid
sample and a flexible reference surface for a non-destructive zeta
potential analysis. Assuming a similar roughness for both sample
and reference surfaces, the assumption of an equal contribution of
both surfaces to the overall zeta potential is appropriate. However,
a sample with severe surface roughness dominates the zeta poten-
tial, and the contribution of the (smooth) reference surface may
become negligible. The same applies for a porous coating or a
swollen material surface.
ζ There is no evidence yet reported for the influence of

roughness on the zeta potential.
 6.8. Measuring time
At the interface between a solid material and an aqueous solution,

various processes take place with different kinetics and thus differ-
ent times required to achieve equilibrium. In this chapter we want
to distinguish time effects related to the principle of the solid sur-
face zeta potential analysis from those where the zeta potential
acts as an indicator for surface or material-related processes such
as wetting, swelling or chemical reactions.
Reliable and reproducible surface zeta potential analysis requires a

completely equilibrated interface between the solid surface and the
62
surrounding aqueous solution. When measuring the corresponding

streaming potential or streaming current we are concerned with the
time-to-equilibrium for
• the formation of the electrical double layer at the solid-liquid

interface,
• the generation of the streaming potential or streaming current
signal
• and the adjustment of the surface charge to any changes in
the aqueous solution (here we primarily focus on changes in
the electrolyte pH).
Electrical double layer
When a solid material is brought in contact with an aqueous

solution, a charge distribution at the solid-water interface is gen-
erated which differs from the charge distribution in the bulk liquid
phase. This interfacial charge distribution is described by the model
of the electrochemical double layer (EDL). The electrical double
layer consists of a stationary water layer at the solid surface and
a diffuse layer, which is dominated by ions with a charge oppo-
nent to the solid surface charge (see chapter 3). The equilibrium of
this diffuse part of the EDL is established instantaneously and will
immediately adjust to changes in the solid surface charge.
Other material-related processes such as wetting or swelling, but

also the formation of solid surface charge by dissociation or pro-
tonation of surface functional groups, may occur much slower. This
is why an equilibration of the solid material in contact with the
aqueous solution for a sufficiently long time is required before start-
ing the streaming potential or streaming current measurement.10
10
The recommended time for this type of equilibration strongly depends on the solid
material and ranges from less than one minute up to 24 hours.
63
Streaming potential and streaming current
The streaming potential and the streaming current are extremely

sensitive to changes in the differential pressure which is generated
when streaming the aqueous solution through a capillary com-
posed of the solid material. Figure 6.10 shows the changes in
the streaming current signal upon small and large changes in the
differe ntial pressure. When changing the pressure continuously,
the streaming current signal immediately follows within the time
resolution of 500 ms of the data recording. When the pressure is
changed considerably (from 750 mbar to 50 mbar at t = 6 s), the
streaming current again changes immediately. We observe an over-
shooting of the final streaming current signal which is caused by
the measuring electrodes. An equilibrium streaming current signal
is established after 1 s.
Fig. 6.10.
Recording of
the response of
streaming current
on smooth and
immediate changes
in the differential
pressure with time.
pH change of electrolyte
When changing the pH of the aqueous solution, the dissociation

or protonation of functional groups of the solid material surface
is affected. The establishment of the corresponding dissociation/
protonation equilibrium is the most time consuming part of solid
surface zeta potential analysis. The required time for equilibration
64
strongly depends on the solid material. Figure 6.11 shows the

equilibration of interfacial charge for a polymer surface when the
electrolyte pH is decreased from pH 6.4 to pH 4.1.11 The streaming
potential follows the change in pH with a lower rate but equilibrates
after less than 1 minute. The rate is not only determined by the dis-
sociation or protonation equilibrium of the surface functional groups
but also by the transport kinetics of acid (added to decrease the
electrolyte pH) towards the solid surface. The commonly applied
rinse time between individual pH titration steps of 3 to 5 minutes
is thus sufficient to ensure the same pH conditions in the bulk
electrolyte solution and at the solid-liquid interface.
Fig. 6.11.
Time dependence
of streaming poten-
tial upon change in
electrolyte pH for a
polypropylene film.
An example for a more complex material behavior is shown in

Figure 6.12. The graph shows the pH dependence of zeta poten-
tial for a microporous silicon carbide filter module. Not only is
the surface area of this filter module much larger than the poly-
mer film used to generate the data shown in Figure 6.11, but the
ceramic surface also takes longer to equilibrate changes in the
electrolyte pH due to a more complex chemistry. The data shown in
Figure 6.12 demonstrates that elongated rinse time between zeta
potential analyses at adjacent pH is required to guarantee that the
electrolyte and interfacial pH coincide.
11
Such extreme changes in the electrolyte pH are not used in a common analysis of
the pH dependence of zeta potential (here the changes in pH are usually less than 0.5
pH units).
65
Fig. 6.12.
pH dependence
of zeta potential
for a microporous
silicon carbide filter
module. The effect
of different rinse
times between zeta
potential analyses
at subsequent
pH demonstrates
the elongated
equilibration at
ceramic-water
interfaces.
Other time-dependent processes
The use of the zeta potential as an indicator for other time-depen-

dent processes mainly focuses on the swelling of natural fibers.
Figure 6.13 shows the change in zeta potential with time for cotton
and regenerated cellulose fibers (Stana-Kleinschek et al., 2001).
The apparent zeta potential, which is determined from streaming
potential measurements and calculated according to Eq. 4.4 in
chapter 4.1, decreases with time during the swelling processes.
The physical background for this observation is explained in
chapter 6.10.
Fig. 6.13.
Time dependence
of zeta potential for
bleached cotton and
regenerated cellulose
fibers (1 mmol/l KCl,
pH 8.5).
66
A second and even more important application of the time depen-

dence of zeta potential is the recording of the kinetics of liquid-on-
solid surface adsorption processes. Such adsorption and
desorption processes introduce a special case for the chemical
modification of a solid surface in contact with an aqueous solution.
The application of the streaming potential and streaming current
measurement for the analysis of adsorption processes is discussed
in more detail in chapter 7.3. Other examples of dynamic processes
are the dissolution of cations and anions of minerals such as metal
oxides, or the oxidation (corrosion) of metal surfaces.
ζ Reliable surface zeta potential analysis requires a

completely equilibrated interface between the solid
surface and the surrounding aqueous solution.
The formation of the electrical double layer at the solid-

liquid interface happens instantaneously.
The streaming potential / streaming current signal

immediately follows changes in the differential pressure.
The required time for equilibration upon any changes in

the aqueous solution like pH strongly depends on the
solid material under investigation.
The zeta potential also serves as an indicator for time-

dependent processes like swelling or adsorption / desorp-
tion.
67
 6.9. Temperature
Most zeta potential analyses are performed at room temperature,

i.e. in the range from 20 °C to 30 °C. Although the individual
measuring parameters that contribute to the zeta potential calcula-
tion, such as solvent viscosity and dielectric coefficient, electrolyte
conductivity and thus the streaming potential or streaming current
themselves depend on temperature, an effect of temperature on
the zeta potential is not observed.
However, the effect of temperature on the kinetics of surface or

interfacial reactions such as the dissociation and protonation of
functional groups as well as adsorption processes cannot be
neglected. In such cases a deviation in the kinetics is not accounted
for by the temperature dependence of the zeta potential but of the
chemical processes (here the zeta potential only serves as a
surface indicator).
ζ Although the individual measuring parameters for zeta

potential calculation like viscosity depend on temperature,
an effect of temperature on the zeta potential is not
observed.
 6.10. Material swelling
The water uptake capability of material surfaces, especially of

bulk materials, has a significant effect on the zeta potential. While
the occurrence and extent of surface swelling is well character-
ized by a comparison of the correct and apparent zeta potential
values calculated from streaming potential and streaming current
measurements, the bulk material swelling cannot be compensated
completely.
68
Figure 6.14 shows the swelling of a polyelectrolyte coating on a

rigid support material. The polyelectrolyte, a polypeptide with
acidic surface groups, exhibits swelling depending on the
electrolyte pH. At a low pH the correct and apparent zeta potential
data coincide. The streaming potential measurement is not affected
by ionic conductance inside the swollen layer, so the apparent zeta
potential is not rated too low. The absence of interfacial con
ductance suggests a compact polyelectrolyte layer. When the pH
is increased, acidic surface groups dissociate and assume negative
charges. Adjacent and equally charged groups introduce electro
static repulsive forces, which provoke the polymer chains of the
polypeptide coating to expand. This expansion or swelling parallels
an introduction of ionic conductance into the polyelectrolyte coat-
ing and a discrepancy between the correct and apparent zeta
potential values at a high pH.
Fig. 6.14.
pH dependence of
apparent and correct
zeta potential for
a poly(L-glutamic
acid) layer coated on
glass. The difference
between the correct
and apparent zeta
potential in the alka-
line range reveals
interfacial con
ductance caused by
enhanced swelling of
the highly charged
polypeptide layer
(Werner et al., 2001).
69
Bulk material swelling has an even more dramatic effect on

the apparent zeta potential, since the bulk material conductance
exceeds the electrolyte conductivity of the aqueous solution by far.
Furthermore, the interface between the swollen material and the
aqueous solution becomes less pronounced and the shear plane of
the electrical double layer (i.e. the location where the zeta poten-
tial is defined) is shifted towards the aqueous phase. The effect
of this shift on the magnitude of the zeta potential is illustrated
in Figure 6.15. While the sign of the zeta potential is not affected
by material swelling, its magnitude decreases with an increasing
degree of water uptake.
Fig. 6.15.
Illustration of the
effect of fiber swell-
ing on the position
of the electrokinetic
shear plane and thus
on the magnitude
of the zeta potential
(adapted from Stana-
Kleinschek et al.,
2001).
The electric double layer and the zeta potential are simplified
models that allow successful descriptions of the majority of surface
phenomena related to surface charge. Material swelling introduces
complexity, which is not explained by these models. The streaming
current, however, is not restricted by boundary conditions of any
model and gives experimental evidence for the effect of bulk
material swelling. Figure 6.16 shows the evolution of the streaming
current coefficient dI str /dΔp with the electrolyte pH for a regenerated
cellulose fiber. The dotted lines indicate the expected evolution of
dI str /dΔp assuming either the absence of swelling or at least its
restriction to the fiber surface. The maximum in the negative
streaming current coefficient and thus in the negative zeta potential
70
that becomes obvious by a pH titration of the surface groups is an

undisputable indicator for bulk material swelling. The concurrent
effect of internal streaming current contribution to the measured
streaming current is impossible to separate (unlike the internal and
external contribution to the streaming current of porous material
discussed in chapter 6.5).
Fig. 6.16.
pH dependence of
streaming current
coefficient dIstr /dΔp
for untreated and
oxidized viscose
fibers. The dotted
lines indicate the
expected evolution
of dIstr /dΔp with pH
in the absence of
swelling.
ζ The water uptake capability of material surfaces, par-

ticularly of bulk materials, has a significant effect on the
zeta potential. While the sign of the zeta potential is not
affected by material swelling, its magnitude decreases
with an increasing degree of water uptake.
71
Measurement capabilities
7. Measurement capabilities
In the past years the solid surface zeta potential has attracted
increasing interest for material characterization. It is no longer
solely used as the indicator for surface charge and the isoelectric
point. The power of the zeta potential to identify the interaction
between dissolved compounds in (an aqueous) solution and solid
material surfaces is now widely recognized.
Studies of adsorption and desorption kinetics and equilibria, the

affinity of simple and complex solutes towards a solid or the alter-
ation of surface charge under different environmental conditions
have developed. Despite these phenomenological studies the
characterization of the solid surface by means of surface charge
and IEP still dominates the possible applications of the solid sur-
face zeta potential.
 7.1. Zeta potential
The zeta potential is primarily used as the indicator for solid sur-
face charge. Although a physical relation exists between the zeta
potential and electrokinetic charge density (Eq. 3.1 in chapter 3),
the zeta potential does not provide quantitative information about
solid surface charge. It is a valuable parameter for the comparison
of material surfaces in terms of their charging behavior in an
aqueous solution as well as of a material surface before and after
surface treatment or modification.
The chart in Figure 7.1 shows the zeta potential data for a selection
of different material surfaces in the presence of 0.001 mol/l KCl
(pH 6). At a neutral pH the majority of natural and technical material
surfaces assumes a negative charge. Chitosan (a polysaccharide
containing amine groups) or heavy metal oxides are representative
examples that exhibit a positive charge.
A comparison of zeta potential data for materials with completely

different properties (swelling, structure, wetting) is not reasonable
72
in practice. Some materials let us determine the correct zeta poten-

tial (polymers, glass) while others give access to an apparent zeta
potential only (natural fibers). However, the comparison of the zeta
potential of a certain series of similar materials such as polymers,
minerals or natural fibers provides valuable information about their
differences in behavior at the surface-water interface.
Fig. 7.1.
Zeta potential of
selected material
surfaces in aqueous
0.001 mol/l KCl
solution at pH 6.
If we take poly(methyl methacrylate), PMMA, and poly(tetra fluoro

ethylene), PTFE, as examples for polymers, we find a difference
in the zeta potential of Δζ = 15 mV with PTFE assuming a higher
negative charge. Although the zeta potential at a single pH does
not explain the nature of the surface charge (see chapter 3.1 for
charge formation principles) it clearly differentiates these two
polymer surfaces and helps to predict consequences that derive
from this difference.
Surface modification processes are even better illustrated by the

corresponding changes in the zeta potential. Let us consider the
deposition of a chitosan layer on a glass plate. The untreated glass
surface is negatively charged and the zeta potential at pH 6
assumes ζ = -30 mV. The zeta potential of chitosan, a polysaccha-
ride with varied molecular weight, is directly determined from the
measurement of electrophoretic mobility. We use chitosan with
ζ = +25 mV. Their charges with opposite signs let us assume that
electrostatic forces contribute to the adhesion of a chitosan layer
on glass. Since the zeta potential is sensitive to the outermost
73
surface, full coverage of the glass surface by chitosan will result in

ζ = +25 mV, i.e. the zeta potential of chitosan in solution. On the
other hand, for example, a zeta potential of ζ = +10 mV obtained
after chitosan coating indicates an incomplete coverage of the
glass surface by chitosan.
ζ The zeta potential is primarily used as the indicator for

solid surface charge. At a neutral pH the majority of
natural and technical material surfaces assumes a nega-
tive charge.
 7.2. Isoelectric point
The information provided by the zeta potential at a given electrolyte

composition (i.e. at a certain pH) is limited, especially for the sake
of solid surface characterization. The pH dependence of the
charging of solid-water interfaces reveals information about the
nature of the charges and thus the chemistry of the surface. The
isoelectric point, i.e. the pH where the electrokinetic charge density
assumes 0 C/m 2 and thus ζ = 0 mV, is an important parameter for
both biological and technical processes and is derived from the
analysis of zeta potential at different electrolyte pH.
The conclusion to be drawn from the different pH dependences of

the zeta potential on the charging mechanism and the nature of
the surface functional groups is illustrated by Figure 6.1 in chapter
6.1. Although this simplified picture of the effect of different sur-
face chemistry on the pH dependence of the zeta potential is only
partially reflected by real material samples, it is a helpful guideline
for data interpretation. Technical sample surfaces are either com-
prised of a combination of acidic and basic groups of different pK
values or a heterogeneous pattern of functionalized (thus hydro-
philic) and hydrophobic surface areas.
A representative example for the continuous transfer of a hydro-

phobic polymer to a hydrophilic material is shown in Figure 7.2.
74
A polyethylene film (PE) was surface-modified by photochemical

treatment (Temmel et al., 2005). Strongly acidic sulfonic acid
groups were introduced successively, with the surface concentration
increasing with treatment time. The PE film surface was thus con-
verted from hydrophobic (water repellent) to hydrophilic. The nature
of the charges represented by the zeta potential changed from
interfacial water ions to dissociated acidic groups bound to the
surface. The sulfonic acid groups attract water molecules that
surround these hydrophilic entities. The total electrokinetic charge
density and thus the (negative) zeta potential decrease. Since
hydroxide ions (OH –) are exchanged by sulfonic acid groups and
(neutral) water molecules, the hydrophobic-hydrophilic transfer is
best observed at a high pH (i.e., at higher concentration of
OH – ions).
Fig. 7.2.
Photochemical
modification of a
polyethylene film.
The introduction
of sulfonic surface
groups increases the
surface hydrophilicity
(Temmel et al.,
2005).
The zeta potential-pH curves may also contain other information

about the material behavior besides the surface charge and the
IEP. Two effects deserve to be mentioned: material swelling and
buffer capacity for acids or bases. Figure 7.3 shows the pH
dependence of the apparent zeta potential for two viscose fibers
with different degrees of oxidation 12 (Biliuta et al., 2013). These
curves differ from the previous data presented in Figures 6.1 and
7.2. We find similarity with the zeta potential for acidic surface
12
The corresponding streaming current data is presented in Figure 6.16.
75
groups (plateau of negative zeta potential at neutral and high pH,

IEP at a low pH) which confirms the presence of hydroxyl (–OH)
and carboxyl groups (COOH) of cellulose. However, the evolution
of the zeta potential is significantly different in the range pH 4-5,
where it first passes a maximum before approaching the plateau
value at a lower negative zeta potential.
The effect of bulk material swelling was already discussed in

chapter 6.10. Here we focus on the information provided by the
zeta potential-pH curves of swollen material, i.e. its use as an indi-
cator for the degree of swelling. The swelling and thus water
uptake capability of a material are related to its hydrophilicity and
structure. As for the photochemically modified polyethylene film of
Figure 7.2, a decrease in the negative zeta potential at a high pH
indicates an increase in hydrophilicity. With enhanced swelling, the
ratio between the maximum negative zeta potential (at a slightly
acidic pH) and the plateau value (at a high pH), ζ max /ζ plateau ,
increases. The shift in the IEP from pH 2.5 for untreated viscose to
pH 1.9 for oxidized viscose demonstrates the increasing contri
bution of carboxyl groups to the negative surface charge.
Fig. 7.3.
pH dependence of
apparent zeta poten-
tial for untreated
and oxidized viscose
fibers.
To confirm material swelling a pH sweep of the zeta potential needs

to be performed. If swelling is already assumed its degree may be
estimated by the zeta potential at a neutral pH only. Figure 7.4
76
shows an example for a different material: human hair with different

degrees of bleaching. The zeta potential was determined in the
presence of 0.001 mol/l KCl (pH 5.6) with the ratio ζ max /ζ plateau
increasing for hair with enhanced bleaching.
Fig. 7.4.
Correlation between
the apparent zeta
potential and the
degree of bleach-
ing of human hair
(0.001 mol/l KCl,
pH 5.6).
The capability of a material to compensate acids or bases added

to the aqueous solution in order to decrease or increase the
electrolyte pH (buffer capacity) does not affect the magnitude (or
even sign) of the zeta potential but, again, the zeta potential-pH
curve. Figure 7.5 shows the attempt of an acid titration of the
mineral calcium carbonate, CaCO 3. The initial pH of the measure-
ment (pH 9) corresp onds to the equilibrium pH of CaCO 3 powder
dispersed in water. The acid (0.05 mol/l HCl) added to the aqueous
solution to reduce the pH is completely digested by the powder
sample. A progress in the pH titration is thus inhibited.
The extent of this effect is determined by the surface area of the

mineral powder that is exposed to the aqueous solution. In the case
of granular mineral samples, pH-dependent surface dissolution
or deposition processes are likely to add to the titration of the
material surface.
77
Fig. 7.5.
pH dependence of
zeta potential for
carbonate sand.
While carbonate in
solution decelerates
the progress in
the pH titration
at a high pH, the
buffer capacity of
the granular media
becomes obvious
around pH 6.
ζ The pH dependence of the charging of solid-water inter-

faces is very important for understanding the chemistry of
surfaces.
The isoelectric point, i.e. the pH where ζ = 0 mV, is

an important parameter for biological and technical
processes.
The pH dependence of the zeta potential may also

reveal information about the solid surface hydrophilicity,
material swelling or buffer capacity for acids or bases.
78
 7.3. Adsorption analysis
The capability of the streaming potential and streaming current

method to record liquid-on-solid surface adsorption and desorp-
tion processes was already discussed in chapter 6.3.
Two approaches exist whose combination is reasonable in order

to obtain detailed information about the affinity of adsorbates on
material surfaces:
• the dependence of the zeta potential on adsorbate con

centration and
• the time-resolved recording of changes in the zeta potential
upon addition of a certain concentration of adsorbate to the
aqueous solution.
Adsorption isotherm
Figure 7.6 shows the effect of a cationic surfactant on the zeta

potential of a glass surface. With increasing concentration of the
surfactant, the negative zeta potential of untreated glass decreases
and reverses its sign at the point of zero charge (PZC, a.k.a. the
point of charge reversal, PCR), i.e. the adsorbate concentration
where the net charge density assumes 0 C/m 2. At an even higher
concentration of the cationic surfactant, the surface becomes more
positively charged. The apparent plateau in the positive zeta poten-
tial indicates saturation of the solid surface by the surfactant. Any
further adsorbate deposited on the glass surface is not detected.
Various parameters contribute to the adsorption characteristics

of a certain adsorbate on a certain material surface: electrolyte
pH (affects the charge of the adsorbate and solid surface), ionic
strength (affects the electrostatic interaction and the conformation
of complex adsorbates), critical micelle concentration (in case of
surfactants), temperature, competitive adsorbate in solution, etc.
79
Fig. 7.6.
Adsorption of the
cationic surfactant
N-cetyl pyridinium
chloride (CPC) on
glass. The point of
zero charge (PZC) at
0.008 ppm CPC is
indicated.
The zeta potential-adsorbate concentration analysis may also be

used to assess better information about the solid surface charge
(the density of surface functional groups). Here the interest is not
on the adsorbate or its interaction with the solid surface, but on the
material characterization (as for the pH titration). Figure 7.7 shows
the dependence of the apparent zeta potential of the viscose fibers
of Figure 7.3 on the concentration of the cationic polyelectrolyte
poly(acryl amide), cPAA. The cPAA concentration is refered to the
weight of the viscose fiber sample used for each measurement.
The oxidized viscose fiber consumes a significantly higher amount
of cPAA than the untreated one before reaching its PZC. This
higher consumption is caused by the larger number of acidic sur-
face functional groups, further enhanced by the better accessib ility
of the inner structure of the stronger swollen fibers. The adsorbate
concentration at the point of zero charge may be converted to
surface concentration of oppositely charged functional groups
which reside in the charged state, i.e. either dissociated or pro-
tonated. Again the pH dependence of the surface charge and the
condition of the adsorbate needs to be taken into account when
applying this method for the quantification of surface functional
groups.
80
Fig. 7.7.
Adsorption of the
cationic polyelectro
lyte poly(acryl amide)
on untreated and
oxidized viscose
fibers.
Besides the parameters of PZC and plateau concentration, more

quantitative information may be drawn from the detailed analysis
of the zeta potential-adsorbate concentration curve. Bellmann et
al. (2007) have discussed the adsorption of cationic surfactants
on negatively charged surfaces in terms of a four-region adsorp-
tion model.
Adsorption kinetics
When recording the zeta potential at different adsorbate con

centration, knowledge of the time for equilibration between
individual adsorption steps is required. Although there exists a rule
of thumb for different adsorbates (fast adsorption of surfactants,
slow adsorption of proteins and other polyelectrolytes), know
ledge of the real kinetics and thus time to equilibrate is obligatory
for accurate measurements. The streaming potential and stream-
ing current are sensitive parameters for recording the kinetics of
adsorption of compounds dissolved in an aqueous solution on a
solid surface.
The experimental approach is rather simple: after addition of a

certain adsorbate concentration to the aqueous solution, the
changes of streaming potential or streaming current are recorded
81
with time. Figure 7.8 shows the adsorption of a cationic surfactant

(a) and a protein (b) on a glass surface. The time scales of these
records and thus the adsorption kinetics are remarkably different
for these adsorbates. The shapes of these curves differ as well.
Surfactant adsorption may be described by first-order kinetics
while protein adsorption is more complex and likely comprised of
two processes with different rates.
Fig. 7.8.
Kinetics of adsorption
(a) of the cationic
surfactant N-cetyl
trimethyl ammo-
nium bromide and
(b) of bovine serum
albumine on glass
monitored by stream-
ing current and zeta
potential, respectively.
ζ The surface zeta potential enables the characterization

of liquid-on-solid surface adsorption and desorption
processes.
The dependence of the zeta potential on the adsorbate

concentration reveals the point of zero charge and infor-
mation about the adsorption mechanism.
The streaming potential and streaming current are

sensitive parameters for recording the kinetics of adsorp-
tion of compounds dissolved in an aqueous solution on a
solid surface.
82
 7.4. Simulation of environmental conditions
The streaming potential method is used for solid surface analysis

under ambient conditions. The exposure of real material sur-
faces to an aqueous solution allows for a direct observation of
the interaction of liquid and solid chemistries. Besides the focus
on the characterization of the solid material surface using a well
defined composition of an aqueous solution, e.g. a 0.001 mol/l KCl
solution, the phenomenological assessment of the behavior of a
solid in a complex aqueous environment is possible.
Although the sensitivity of the streaming potential and streaming

current method restricts the application of aqueous solutions with
respect to ionic strength (see chapter 6.2.), pH (mainly due to the
effect of a high acid or base concentration on the conductivity
of the aqueous solution) or chemicals that poison the electrode
material, there are numerous applications in which phenomenologi-
cal studies lead to valuable information.
Prominent examples are membrane surface analyses in the

presence of seawater or the monitoring of the surface charge of
an implant material in a protein solution. Another category of com-
plex solute-surface interaction studies involve surfactant solutions
and emulsion formulations in cosmetics for hair and skin care and
detergents for textile laundry and household cleaners.
It is obvious that the zeta potential is mainly used for industrial

rather than academic purposes with regard to the observation
of solid surface phenomena in a complex aqueous environment.
Scientific literature on the use of the solid surface zeta potential
for the simulation of environmental conditions is therefore scarce.
Oo and Ong (2010) have applied model seawater (an aqueous

NaCl solution with a concentration up to 0.17 mol/l) to simulate
the effect of high salinity on the zeta potential of commercial thin-
film composite membranes for nanofiltration and reverse osmosis.
The measurement of streaming potential and streaming current in
83
high salinity solution is indeed feasible as illustrated by the results

shown in Figure 7.9.
Fig. 7.9.
Streaming potential
for polypropylene
measured in
aqueous 0.15 mol/l
and 0.2 mol/l KCl
solution. The
zeta potential
is calculated as
ζ = –13.1 ± 0.6 mV
in 0.15 mol/l KCl and
ζ = –11.3 ± 0.1 mV
in 0.2 mol/l KCl.
Alkafeef and Alajmi (2006) reported streaming potential data for

rock core samples using non-aqueous solvents such as toluene,
acetone or methanol instead of water. Although the use of solvents
with lower polarity than water is possible to some extent (e.g.
ethanol) 13, the interpretation of zeta potential data becomes com-
plex. The question of charge formation in non-aqueous solvents
is still unresolved, so the formation of the electrical double layer
and the solid-liquid interface remains unclear. Furthermore, the
maintenance of water-free solvents is challenging. On the other
hand, traces of water in non-aqueous solvents will likely influence
the charge formation at the interface and thus the streaming poten-
tial data.
Jachowicz and Berthiaume (1989) investigated the effect of a

commercial silicone emulsion on untreated and modified human
hair. In this application the zeta potential is primarily used to
indicate the adsorption and desorption processes of liquid compo-
nents on hair fibers of different origin (Jachowicz et al., 1993).
13
The equations used for zeta potential calculation (chapter 4.1) contain the viscosity
and dielectric coefficient of the solvent and thus do not restrict the application of the
streaming potential and streaming current method to an aqueous solution.
84
A quantitative analysis of the kinetics of competitive adsorption

and desorption processes is also possible, provided that the
number of involved adsorbates is limited.
ζ The streaming potential method can be employed under

ambient conditions, where material surfaces are exposed
to a complex aqueous environment. Such studies allow
the phenomenological assessment of the solid material’s
behavior and are mainly used for industrial purposes.
85
Applications
8. Applications
The information provided by the solid surface zeta potential and
thus the application of the streaming potential and streaming
current method has proven valuable for a variety of applications.
The applicability of solid materials for technical processes is
determined by their surface properties, among many other para
meters. Zeta potential analysis provides information on the inter-
facial behavior of solids, especially if water or an aqueous solution
determine the material’s surroundings. Interfacial properties are
driven by the outermost solid surface, so a measuring technique
scaling the surface to the molecular level is required. Despite of
these needs and the benefit of the streaming potential method,
the solid surface zeta potential was first employed for solid surface
analysis only 30 years ago.
After the introduction of the zeta potential by Marjan von

Smoluchowski in 1905 (see chapter 2 for a historical review) and
prior to the development of the first commercial streaming potential
apparatus, the streaming potential and streaming current method
was employed to access the surface charge of cellulose fibers
(Goring and Mason, 1950; Chang and Robertson, 1967; Onabe,
1978), quartz and minerals (Fuerstenau, 1956), polymer fibers
(Mossman and Mason, 1959), glass (Jednacak et al., 1974), human
teeth (Kambara et al., 1978), hair (Parreira, 1980) and a poly-
mer membrane (Kaneko and Yamamoto, 1976). It took almost a
century from the description of the zeta potential by Smoluchowski
to the development of a prototype streaming potential apparatus
for commercial use by Jacobasch and co-workers in the 1980s
(Jacobasch and Börner, 1983). From this time onwards the stream-
ing potential continuously established itself as a solid surface
analysis and adsorption monitoring parameter.
The intention of the zeta potential analysis for material surface

characterization has not changed much in state-of-the-art mate-
rial research and engineering. Obviously solid materials experienc-
ing aqueous solutions in their application drive the requests for
86
Applications
surface charge analysis. Electrostatic interaction, either repulsion

or attraction, between the solid surface and solutes in water
determines the performance of membranes for water treatment,
the acceptance of implants by the human body or the adhesion of
dyestuff on textile fabrics.
Another topic in zeta potential analysis is the investigation of the

effect and efficiency of surface modification processes and sur-
face treatment of materials. Even if the solid material is not used in
contact with an aqueous solution after modification, the zeta poten-
tial is used as an indicator for changes in the surface chemistry.
Since such processes predominantly affect the outermost solid
surface, the sensitivity of the streaming potential is unsurpassed
among surface analytical methods.
Finally, the capability of the streaming potential method to monitor

liquid-on-solid surface adsorption processes makes it a valuable
technique to study such processes with real materials.
 8.1. Membranes and filters
A variety of different filtration and membrane processes for

separation and purification have been developed. The challenge for
all membrane and filter applications is the optimization of rejection,
flux, energy consumption, lifetime, etc. Membrane and filter para
meters such as pore size, porosity, surface roughness, wettability,
and surface charge determine the applicability of the filter or mem-
brane to a different extent.
Surface charge is the driving force for the retention in depth

filtration, ultrafiltration and nanofiltration and is therefore directly
linked to the membrane and filter performance. An obstacle in
filtration processes is the tendency of membranes and filters to
the formation of biofilms, which is commonly termed membrane
fouling. Fouling has various origins and primarily affects membrane
processes, to different degrees. Again membrane roughness,
87
Applications
hydrophilicity and charge are responsible for the promotion or

suppression of fouling processes. The attempt of researchers in
this field is to modify the surfaces of existing membranes using
different treatment processes. These modifications affect the outer
surface of membranes and require a surface-sensitive analytical
technique for characterization and quality control.
In the field of membranes and filters the zeta potential is therefore

important to understand filter and membrane rejection for selected
filtration processes, to optimize membranes with reduced fouling
propensity and to characterize membrane surface modification
processes. Figure 8.1 compares the filtration spectrum with the
applicability of the zeta potential analysis.
Fig. 8.1.
Applicability of the
solid zeta potential
for the analysis of
membrane surface
charge.
Typical samples
Membranes and filters are made of different materials and exist

in different shapes. The most common forms are polymer mem-
branes and ceramic filters. We find flat sheet (FS) and hollow fiber
(HF) membranes and filters. Membranes can be made of a single
material or prepared as a composite of different materials. Flat-
sheet microfiltration (MF) membranes are symmetric in terms of
their pore size distribution and applicable for filtration using both
88
Applications
sides. Ultrafiltration (UF) membranes usually have an asymmet-

ric pore size distribution and occur as FS and HF membranes.
Nanofiltration (NF) and reverse osmosis (RO) membranes are com-
posites of a dense polyamide-based thin film deposited on a poly-
urethane UF membrane. NF and RO membranes are mechanically
supported by a polyester nonwoven. In this case the thin poly
amide-based film that faces the feed solution is the surface of
interest for characterization. New developments include pressure-
retarded osmosis (PRO) and forward osmosis (FO) membranes.
Depending on their application for desalination or energy genera-
tion, both sides of these composite membranes may be of interest.
Finally, ceramic membranes for microfiltration and ultrafiltration
have certain benefits due to their enhanced thermal and chemical
resistance compared to polymer membranes. Ceramic membranes
usually exhibit a tubular shape with single or multiple channels.
Literature review
The majority of scientific literature published on solid surface zeta

potential covers polymer membranes for various water treatment
applications such as microfiltration, ultrafiltration, nanofiltration,
reverse osmosis and, very recently, for pressure-retarded and
forward osmosis processes. Other applications involve the analysis
of membranes used in hemodialysis and for biotechnological
processes. Besides membranes made of polymers, the use of
ceramic membranes is becoming increasingly popular for water
treatment application. Ceramic membranes introduce an additional
challenge to the streaming potential and streaming current
measurem ent due to their complex geometry.
A complete review of corresponding scientific literature exceeds

the scope of this booklet. A selection of research groups and
examples of their papers that introduce pioneering work in the field
of membrane characterization by means of zeta potential are there-
fore highlighted.
89
Applications
Elimelech et al. (1994) were the first to intensively characterize the

surface zeta potential of cellulose acetate and composite poly
amide membranes for reverse osmosis. They already looked at the
effect of membrane fouling by humic substances on the zeta poten-
tial. Childress and Elimelech (1996) extended this research by the
investigation of the cooperative effects of divalent ions and humic
acid on polymeric nanofiltration and RO membranes. Among the
solutes they used surfactants to elucidate their effect on the mem-
brane chemistry. In another paper, Childress and Elimelech (2000)
correlated the performance of a NF membrane with the zeta poten-
tial. Vrijenhoek et al. (2001) used the zeta potential as an indicator
for the initial rate of membrane fouling. Deshmukh and Childress
(2001) studied the effect of feed water taken from different rivers
on the zeta potential of RO membranes.
Nghiem and co-workers focused on the rejection of pharma

ceutically active compounds by NF membranes (Simon et al., 2009;
2012). The group of Fane has recently developed HF membranes
for forward osmosis (Setiawan et al., 2011; 2012). Szymczyk
et al. (2006) have specialized in the electrokinetic character
ization of ceramic membranes. Bernstein et al. (2013) used poly
electrolyte coatings to trigger the rejection by UF membranes. The
application of polyelectrolyte multilayers to enhance the selectivity
for the separation of water and alcohol mixtures already has a long
history (Lukas et al., 1997). Important contributions to membrane
development are also added by the Institut Européene des Mem-
branes (Gassara et al., 2013) and the University of Texas at Austin
(Sagle et al., 2009).
In the early days of membrane research the unavailability of

commercial instruments for membrane zeta potential analysis led
various research groups to building their own devices. Nyström et
al. (1989) and Pontié et al. (1997) have contributed valuable zeta
potential data using their home-made streaming potential appara-
tuses.
90
Applications
Monitoring of membrane fouling
Figure 8.2 shows the change in the zeta potential of a NF mem-

brane after filtration of potable water for 24 hours (Comerton at al.,
2008). Transmembrane pressure and flux were maintained during
the cross-flow filtration process. Nevertheless, the zeta potential
indicates a significant change in the surface charge and chemistry.
The negative zeta potential of the sampled NF membrane decreases
at a high pH and the IEP shifts towards the acidic range. These
trends tell us that the polymer membrane surface is rendered more
hydrophilic, most likely due to the deposition of humic substances
or colloidal silica.
Fig. 8.2.
pH dependence of
zeta potential for
NF-270 membrane
compacted by 24
hours of filtration
of deionized water
(clean) and potable
water (Lake Ontario,
fouled).
Prediction of virus retention
Depth filtration using MF membranes is the process of choice to

remove colloids and viruses when only low transmembrane
pressure is applicable. The electrostatic attraction of colloids to the
membrane pore wall drives the separation. Figure 8.3 compares
the zeta potential of two diatomaceous earth (DE) filters with the
surface charge of a typical virus (indicated by its IEP at pH 4). The
plain DE filter is hardly applicable to remove viruses efficiently. The
retention for MS2 bacteriophages is indeed only less than 90%
91
Applications
(Wegmann et al., 2008). Modification of the DE ceramic with zirco-

nia shifts the IEP to pH 9 and thus renders the pore surface charge
positive at the pH of ground water. The retention for MS2 increases
to 99.9999 9 %.
Fig. 8.3.
pH dependence of
zeta potential for
untreated and zirco-
nia-modified DE filter.
The IEP of MS2 as a
representative virus
is indicated.
 8.2. Biomaterials
The term biomaterials covers a tremendously large range of

materials. In principle any material (polymer, ceramic, metal) that
gets exposed to the human body may be considered a biomaterial
and thus has to comply with well defined interfacial properties
(Williams, 2009). When using the solid surface zeta potential for the
study of these interfacial properties, we refer to the “classical” bio-
materials such as artificial implants. With this restriction we still find
a vast variety of applications such as titanium and stainless steel
implants for dental surgery, biodegradable polymer scaffolds for
tissue engineering, hydroxyapatite or alumina ceramics as a bone
substitute, or cardiovascular grafts made of polymer nonwovens.
The surface characterization of biomaterials is closely related to

the study of protein adsorption processes on solid surfaces. The
exposure of a biomaterial surface to an aqueous solution, which
contains proteins and other biomacromolecules, makes the zeta
92
Applications
potential an important parameter to predict the material’s bio

compatibility.
Typical samples
Biomaterials presumably comprise the widest range of samples for

solid surface zeta potential analysis. Artificial implants are made of
stainless steel or titanium, if mechanical strength and durab ility are
required (dental screws, joints). Polymers offer flexib ility and dura-
bility, such as ePTFE or polyesters for cardiovascular grafts. Bio-
degradable polymers are used as scaffolds for tissue regeneration.
Polysulfone is the polymer of choice for hemodialysis membranes.
Poly(vinyl chloride) is used for medical tubing. Acrylate-based
hydrogels are the base material for soft contact lenses. Ceramics
such as alumina and hydroxyapatite are used for bone recovery.
Coatings of biopolymers such as polysaccharides and polyp eptides
are applied to improve the biocompatibility of standard metals and
man-made polymers.
Literature review
While the Romans and Chinese already applied gold as a tooth

replacement material in ancient times, the targeted development of
biomaterials has only started a couple of decades ago. The solid
surface zeta potential was discovered as a valuable param eter for
biomaterials surface characterization even more recently. In 1978
Kambara et al. reported the zeta potential of tooth enamel. The
group of Busscher assigned the surface charge an important role
for bacterial adhesion on human teeth (Weerkamp et al., 1988).
Unfortunately a commercial streaming potential analyzer was
not available at that time, so researchers had to grind enamel
and dentin to assess its zeta potential from the measurement of
electrop horetic mobility. Werner et al. (1995) applied the stream-
ing potential for the inner surface characterization of hemodialysis
membranes. Their approach to probe the inner surface by streaming
93
Applications
an aqueous solution through the membrane capillaries is still in

use today. Picart et al. (2001) monitored the evolution of the zeta
potential during the buildup process of a poly(L-lysine)hyaluronic
acid multilayer. Other polypeptidepolysaccharide multilayer for-
mation was studied by Grohmann et al. (2011). Roessler et al.
(2002) characterized the oxide layer of titanium alloys using the
streaming potential and the streaming current methods. Indest et
al. (2006) investigated the effect of collagen and heparin coating of
polyester vascular grafts. Amaral et al. (2007) determined the zeta
potential for chitosan with different degrees of deacetylation, which
they suggested as a biodegradable scaffold for tissue engineer
ing. Safinia et al. (2007) used atmospheric plasma to increase the
surface energy and thus the biocompatibility of polymer foams.
The complex shape of these foams leaves only the zeta potential
to assess the change in the hydrophilicity which correlates with
the surface charge (Temmel et al., 2005). Diamond-like coating
(DLC) is another surface layer that offers satisfying biocompatibility
(Jelinek et al., 2010a; 2010b). Biosensors can also be considered
as in vitro biomaterials. An interesting approach is presented by
Schrems et al. (2011) who use so-called surface-layer proteins as
a support for lipid bilayer membranes. The investigation of bio-
materials’ zeta potential is accompanied with the study of protein
adsorption kinetics on solid surfaces. Norde and Rouwendal (1990)
and Zembala and Dejardin (1994) were among the first to record
these kinetics by means of changes in the streaming potential.
Adsorption of albumin on titanium
The adsorption of proteins on biomaterial surfaces is a crucial step

towards the acceptance of an artificial implant by the human body.
The solid surface zeta potential is a direct indicator for the kinetics
of liquid-on-solid surface adsorption processes. Figure 8.4a shows
the charging behavior of a titanium disk in an aqueous solution at
different pH values. A native titanium oxide layer covering the
titanium metal disk introduces an amphoteric surface with an IEP
at pH 4.2. The adsorption of the protein bovine serum albumine
94
Applications
(BSA) follows complex kinetics (Figure 8.4b) with a fast initial

process and a second process with a lower rate. After adsorption
equilibrium is achieved, the charge characteristics of the BSA layer
attached to the titanium surface can be recorded and complies
with the charging behavior of BSA in solution (Figure 8.4a). We
conclude that BSA covers the complete titanium disk and the
protein molecules are randomly oriented.
Fig. 8.4.
(a) pH dependence
of zeta potential
for titanium disk
before and after BSA
adsorption.
(b) Adsorption
kinetics of BSA on
titanium surface.
Hemodialysis membranes
A benefit of the solid surface zeta potential analysis is its application

to different shapes of a solid material. This property is used to
assess information about the surface charge and thus the surface
functionality inside polymer capillary membranes used for hemo
dialysis. The modification of the inner surface of poly(ethersulfone)
(PES) hollow fiber membranes with anchor groups for binding bio
compatible macromolecules such as heparin is confirmed by the
zeta potential. Figure 8.5 shows the change in the inner surface
charge of PES capillary membranes after grafting of amine function
alities and subsequent binding of heparin molecules. The hemo
dialysis membranes are arranged in a bundle and supported by the
polyurethane resin, which is used for the hemodialysis modules.
95
Applications
Fig. 8.5.
pH dependence of
zeta potential for
the inner surface of
poly(ethersulfone)
hollow fiber mem-
branes. The effect
of grafting of amine
groups and the sub-
sequent covalent
binding of heparin
is confirmed by
the corresponding
changes in the zeta
potential.
 8.3. Semiconductor
Wet chemical processes in the manufacturing of semiconductor

devices such as microelectronics or sensors introduce an inter
facial charge to the wafer surface, which triggers the effects
and efficiency of such processes. A prominent example for such
processes is the chemical-mechanical planarization (CMP) and the
post-CMP cleaning. Slurries of ceramic particles with a size in the
range of several 100 nm and complex composition are exposed to
the wafer surface. The charge of both the nanoparticles and the
wafer surface determines the electrostatic interaction. Attractive
forces lead to a strong adhesion of oppositely charged particles
that remain adsorbed on the wafer surface and are tedious to
remove. The optimization of the CMP slurry is thus important and
the knowledge of the surface charge of the corresponding wafer
surface is essential.
Another application of the zeta potential in the field of semi

conductor substrates is the deposition of self-assembled mono
layers (SAM) to tune the surface chemistry without changing the
wafer thickness and altering the electrical properties. The sensitivity
of the zeta potential to the outermost solid surface makes this
parameter best suitable to monitor the quality of SAMs.
96
Applications
Typical samples
Silicon wafers with thin-film coatings such as silicon oxide of

different grade (native, polysilicon, thermally grown, plasma-
etched), silicon nitride, but also metal layers (copper, gold, tungsten)
are certainly the most prominent samples for solid surface zeta
potential analysis in the field of semiconductor application. Polymer
layers (e.g. insulating polymer coating, photoresist for lithography)
on silicon wafers comprise another type of sample surface. Besides
silicon and more recently germanium wafers, auxiliary devices used
in semiconductor processing such as photomasks but also CMP
pads or brushes for cleaning are exposed to the aqueous solutions
and must not transfer particles of contaminants among wafer
batches.
Literature review
As opposed to most other application areas for the solid sur-

face zeta potential, the research and development of semicon-
ductor materials and processes is primarily focused on industry.
The number of scientific papers that combine semiconductors
and solid surface zeta potential is therefore rather scarce. Bousse
et al. (1991a; 1991b) applied the streaming potential method for
the analysis of tantalum oxide and silica films deposited on silicon
wafers and of silicon nitride thin films. Jan and Raghavan (1994)
related the number of polystyrene model particles deposited on
a silicon nitride wafer to its zeta potential. Hayes et al. (1991)
looked at the changes in the surface zeta potential with increasing
coverage by silica nanoparticles. Drechsler et al. (2006) compared
the zeta potential of a photoresist film before and after exposure to
UV radiation and to a cationic surfactant.
97
Applications
Oxidation of silicon nitride wafer
The sensitivity of silicon nitride to oxidation in air is demonstrated

by the zeta potential data shown in Figure 8.6. A single-side
polished (100) silicon wafer with a silicon nitride film of 1000 Å
thickness was stored in wafer cassettes under ambient conditions.
The IEP at pH 4.0 indicates an inert behavior of the silicon nitride
wafer in an aqueous solution (refer to chapter 6.1), so a saturated
Si–N–Si surface can be assumed. After dipping the Si 3N 4 wafer in
a dilute HF solution and repeating the measurement, the IEP was
significantly shifted to a higher pH. We therefore assume that the
surface of the silicon nitride wafer, which was stored in an ambient
environment, was partially oxidized. When etching the as-received
silicon nitride wafer in a Piranha solution (H 2 O 2 H 2 SO 4 , room
temperature), followed by a dip into a dilute HF solution, the IEP is
further increased. We explain this observation by the removal of
organic contaminants (which prevented access of HF to SiO 2 in the
first cleaning cycle) in a Piranha solution accompanied by an
oxidation of the Si 3 N 4 surface. This oxide layer is then efficiently
removed by HF.
Fig. 8.6.
pH dependence of
zeta potential for
silicon wafers with
a silicon nitride top
layer. The effect
of different wet
chemical etching on
the surface charge
and IEP is demon-
strated. The zeta
potential of a silicon
oxide film is shown
for comparison.
98
Applications
 8.4. Natural and man-made fibers
Cellulose fibers were among the first samples whose zeta poten-
tial was intensively studied using the streaming potential method.
Based on the analysis of random plugs shaped from cellulose pulp,
cotton, and related fibers, Fairbrother and Mastin (1925), Goring
and Mason (1950), and Chang and Robertson (1967) introduced
practical approaches to compensate the effect of interfacial con-
ductance on the zeta potential.
The processing of cotton for textiles consists of several steps

which affect the surface charge and the accessibility of this cellu-
lose fiber. The different effects of process conditions for scouring,
bleaching or mercerization on the zeta potential of raw cotton
have been studied by many researchers (compare Luxbacher,
2012, for a literature review). The surface charge is decisive for
the subsequent application of dyestuff but also for the more recent
applications of gauze and other fibrous materials in medicine.
A different application of the zeta potential for the surface charge

analysis of fibers extends to composite materials in which glass or
carbon fibers are used as a reinforcement of the polymer matrix.
These inorganic fibers require an appropriate pre-treatment to
increase their surface compatibility towards the organic surround-
ings. Adhesion promoters such as silanes ensure the bonding of
silica fibers to polymers and thus the mechanical reliability of the
composite material. The quality of silane coating of glass fibers
is best assessed by the solid surface zeta potential. Recently,
plant waste fibers were investigated for their use as reinforcing
material. Again silanes are used to increase the fibers’ compatibility
with polymers and the zeta potential analysis to qualify the sizing
process.
We should not forget about human hair as an important natural

fiber. For the application of the solid surface zeta potential, the use
of human hair to test the effectiveness of hair-care products such
as shampoos and conditioners is discussed in chapter 8.5.
99
Applications
Typical samples
The zeta potential of cotton, viscose and other lignocellulosic fibers

has been investigated in detail in the past 20 years. The surface
charge of glass and carbon fibers is primarily important for their
application in light-weight composite materials. Fibers made of
different polymers add another class of fibrous samples for zeta
potential analysis.
Literature review
Among natural fibers, cotton is by far the fiber sample whose

zeta potential has been investigated most extensively. Pusic et al.
(1999) reported the effect of scouring, bleaching and mercerization
of raw cotton on the surface charge. The effect of different cleaning
agents for the extraction of raw cotton impurities such as pectins
and waxes was investigated by Ribitsch et al. (1996; 2001).
Ribitsch et al. (2001) also compared the electrokinetic properties

of cotton with the regenerated cellulose fibers viscose, lyocell and
modal, using the changes of zeta potential with exposure time to
aqueous solutions to study the kinetics of fiber swelling (Stana-
Kleinschek et al., 2001).
The swelling characteristics and the correlation with the moisture

content of natural cellulose fibers was investigated in detail by
Bismarck et al. (2002). Inglesby et al. (2005) applied the solvent
extraction method to alter the zeta potential of rice straw. Jute
fibers were surface-modified by silanes as a possible source for
reinforcing material (Bellmann et al., 2005). Pothan et al. (2002)
applied the same strategy to banana fibers.
100
Applications
The complexity of cellulose fibers
The zeta potential of cellulosic fibers has been reported since the
early days of the streaming potential analysis. Despite of the com-
plex behavior of cellulose fibers (porous structures with outer and
inner surface, high swelling propensity in water) and the restriction
to the apparent zeta potential, the effect of fiber treatment clearly
becomes evident from streaming potential analysis. Figure 8.7
compares the pH dependence of the apparent zeta potential for
cotton linter and cellulose pulp originating from a hardwood tree.
The isoelectric point at pH 2.3 for both cotton linter and hardwood
pulp indicate very similar surface chemistry while the decrease in
the negative zeta potential at a higher pH reflects the enhanced
swelling capacity of the pulp sample. Swelling increases the
accessibility of functional groups located at the inner surface of the
cellulose fiber. The titration with a charge complexation compound
such as the cationic polyelectrolyte poly(acryl amide), cPAA, reveals
the higher ion exchange capacity of hardwood pulp. The point-of-
charge reversal occurs at higher cPAA concentration and accounts
for an increased consumption of the cationic substrate by the pulp
fibers.
Fig. 8.7.
(a) pH dependence
cotton linter and
hardwood pulp.
(b) Determination of
the point-of-charge
reversal for cotton
linter and hardwood
pulp from titration
with poly(acryl
amide), cPAA.
101
Applications
Sizing of glass fibers
Glass fibers show a negative zeta potential in an aqueous solution

due to the dissociation of the acidic silanol functional groups. The
IEP at pH 2.5 and the plateau in negative zeta potential starting at
pH 6 indicate the remarkable acidity of these groups. Glass fibers
therefore behave hydrophilic and thus repel polymer resin; they
need to be sized prior to their application as reinforcing fibers in
composite materials. The sizing agent is a complex mixture con-
taining silanes, which introduce the compatibility to polymers.
Figure 8.8 compares the zeta potential for untreated glass fibers
with sized fibers and with glass fibers treated exclusively with an
aminosilane. We conclude that this aminosilane does not adsorb as
effectively on the glass fiber when supplied within the sizing agent
and assume competitive adsorption by other components of this
sizing mixture such as surfactants.
Fig. 8.8.
pH dependence of
zeta potential for
glass fibers with-
out treatment, after
sizing, and modified
with aminosilane
(AMEO).
102
Applications
 8.5. Cosmetics and detergents
The field of cosmetics and detergents is different from other

applications. Here the main focus is on the properties of emulsions
rather than on a solid material surface. However, emulsions applied
in cosmetics and detergency, such as shampoos and conditioners
for hair care, soaps and lotions for skin care, surfactant solutions
for dishwashing or detergents for laundry interact with solid sur-
faces. The aim of the zeta potential analysis is therefore to gain
information about the surface functionality of hair or skin for the
development of cosmetics formulations, glass, metal and ceramics
for household cleaners, or textile fabrics for laundry detergents
and textile softeners. Another approach of the streaming poten-
tial method is the study of liquid-on-solid surface adsorption and
desorption processes. The interaction of dissolved compounds
contained in emulsions with solid surfaces is driven by such
adsorption processes. The kinetics of the adsorption process and
its dependence on adsorbate concentration in solution provides
valuable information for better understanding and thus developing
more effective emulsion formulations.
Typical samples
The benefit of the streaming potential analysis is definitely the

use of real material surfaces to observe the change in the sur-
face properties, represented by the surface charge, in intera ction
with real emulsions. Bundles of hair fibers and artificial skin are
substrates to evaluate the effectiveness of hair care and skin care
products. Glass, porcelain or stainless steel are materials for test-
ing dishwashing agents. Polymer and ceramic surfaces may be
exposed to household cleaners. Fabrics of different composition
may be employed to investigate the activity of detergents and
softeners.
103
Applications
Literature review
Cosmetics and detergents are certainly application areas for the

zeta potential analysis primarily focused on consumer goods. The
use of the streaming potential therefore follows a phenomenological
visualization of solid-liquid interfacial processes of adsorption and
desorption rather than an in-depth scientific approach. Most of
the literature in this application area deals with the analysis of
human hair. Parreira (1980) and Jachowicz and Berthiaume (1989)
reported the IEP of virgin hair at pH 3.4. Jachowicz et al. (1985)
further investigated the time and concentration dependences of
the adsorption of polyelectrolyte and surfactant molecules on hair.
There is quite a large amount of papers on textile fabrics but only
few that focus on laundry application (Luxbacher et al., 2008;
Agarwal et al., 2012; Luxbacher et al., 2012).
Simulation of a hair washing cycle
Figure 8.9 shows the changes in the streaming potential of a ran-

domly arranged plug of virgin human hair upon the addition of
shampoo and conditioner. The baseline at ΔU = –30 mV represents
the negative charge of virgin hair in an aqueous solution. After 5
minutes, shampoo was added and immediately adsorbed on the
hair fibers. After another 5 minutes the hair treated with shampoo
was rinsed with an aqueous solution again, which removes
shampoo and returns the hair fibers to their original condition. The
addition of conditioner at t = 15 min provokes a fast adsorption
process and reverses the sign of the surface charge. Another rinse
with an aqueous solution after a dwell period of 5 minutes confirms
the adhesion of the conditioner on human hair.
104
Applications
Fig. 8.9.
Recording of the
changes in the
streaming potential
during a simulated
hair washing cycle.
Washing efficiency in textile laundry
Test stripes of stained fabrics are commonly applied to evaluate

the cleaning efficiency of detergents. Figure 8.10 shows the zeta
potential of a raw cotton fabric, which was stained with blood.
The complex evolution of the zeta potential with electrolyte pH
indicates the adsorption of blood proteins on the fabric surface.
Washing of the blood-stained raw cotton fabric with a standard
detergent has an effect on the distribution of the stain on the fabric
but obviously does not clean the fabric efficiently. The addition of
the enzyme amylase to the detergent has a stronger effect on the
stain removal. We speculate that the enzyme further removes some
contaminant of the raw cotton since the zeta potential approaches
that for bleached cotton.
Fig. 8.10.
pH dependence of
zeta potential for raw
cotton fabric stained
with blood and
washed with standard
detergent. The
enhancement of the
cleaning after addition
of the enzyme
amylase is indicated.
105
Applications
 8.6. Polymers
Polymers and polymer surface modification contribute to all

application areas listed above. Polymer membranes and filters
are used for water treatment, biodegradable polymer implants are
found among biomaterials, photoresist (polymer) films are used
in lithog raphy for semiconductor processing, polymer fibers get
blended with cotton for textile fabrics, and polymer surfaces are
exposed to household cleaners in detergent applications. In this
chapter we focus on the surface activation of technical polymers,
e.g. to improve their adhesive properties for printing inks, their
wettability for coatings or their ability for grafting antimicrobial
chemicals.
Polymer surface modification using different technologies such

as flame treatment, corona discharge or plasma activation intro-
duces functional groups which obtain a certain charge in contact
with an aqueous solution. The functional groups render the treated
polymer surface hydrophilic, so the effect of polymer surface modi-
fication can be evaluated qualitatively using a water contact angle
measurem ent. The zeta potential delivers a more quantitative
analysis of the origin of the increased hydrophilicity, thereby
correlating with the water contact angle for a series of modi
fication processes on similar polymers. Furthermore, the stability
of the modification indicated by the availability of surface functional
groups may be monitored with time when the polymer surface is
stored in an aqueous solution and air, respectively. The speed and
reversibility of hydrophobic recovery (Daschiel et al., 2008) are thus
experimentally accessible.
Typical samples
Samples include films, foils, plates, fibers, granular media and

coatings of all kinds of technical polymers.
106
Applications
Literature review
Since the fields of application of polymers are manifold, one can

expect an enormous source of information contained in the scientific
literature. Churaev et al. (1992) coated the inner surface of a glass
capillary with a polystyrene film to measure streaming potential
with a well defined geometry of the streaming channel. Kuehn et
al. (1986) correlated the zeta potential obtained for various polymer
plates with the corresponding water contact angle. Grundke and
Jacobasch (1992) and Jacobasch et al. (1993) characterized the
activation of polymer surfaces for the improvement of lacquer
adhesion in terms of the surface zeta potential. Zimmermann et
al. (2001; 2009) derived an explanation for the origin of interfacial
charge at the polymer-water interface. Temmel et al. (2005) demon
strated the effect of increasing surface conc entration of sulfonic
acid groups on the zeta potential of polye thylene. Kolska et al.
(2013) summarized recent findings in the zeta potential of various
polymer surfaces and its changes upon polymer surface activation.
Lützenkirchen et al. (2008) and Preocanin et al. (2012) focused on
the interface of Teflon® with an aqueous electrolyte solution.
Monitoring polymer surface activation
Industrial-scale processes for polymer surface activation involve

flame treatment, corona discharge, and more recently plasma
treatment. Although the efficiency and quality of the surface
functiona lization by these techniques differ significantly, the trend
in the zeta potential is changing in a similar manner. As shown in
Figure 8.11 for flame treatment of a polypropylene-rubber blend
and for the plasma activation of poly(ethylene terephthalate), the
negative zeta potential in the alkaline pH range decreases and the
isoelectric point is shifted from pH 4 for the pristine polymer sur-
face to a lower pH. A comparison with the effect of controlled
grafting of acidic groups onto a polyimide film confirms that the
introduction of oxygen-containing functional groups gives rise to
107
Applications
the shift in the IEP. The decrease of the negative zeta potential is
assigned to the increasing hydrophilicity of the treated polymer
surface (cf. chapter 3.1).
Fig. 8.11.
Changes in the
pH dependence of
zeta potential after
different activation of
polymer surfaces.
(a) Flame treatment of

polypropylene-EPDM
rubber blend.
(b) Plasma activation

of poly(ethylene
terephthalate).
(c) Grafting of
carboxylic acid
groups on polyimide.
 8.7. Minerals
The characterization of minerals’ surface charge is among the

oldest and thus most frequently reported applications of the zeta
potential. Although there are different needs in the research of
mineral surfaces and their interaction with dissolved compounds in
aqueous systems, the major focus is on the process of floatation.
Other applications for the zeta potential analysis of minerals are
found in the studies of metal corrosion, the development of filtration
media, the improvement of enhanced oil recovery, and certainly in
the processing of ceramics.
The analysis of mineral samples is often at the boundary between

the different measuring techniques of electrophoretic mobility,
streaming potential, and electroacoustics. The primary property of
the mineral sample that determines the method of choice is the
particle size, followed by the hygroscopic behavior of the mineral
grains. The streaming potential method requires a minimum par-
ticle size which ranges from 25 µm for individual particles to 50 µm
108
Applications
for particles which form aggregates in contact with water and thus
suppress the permeability of a powder bed.
Typical samples
Samples cover granular powders of natural and synthetic minerals,

porous metal oxide ceramics, and platelets of single crystals.
Literature review
The surfaces of minerals show complex behavior when in contact

with an aqueous solution. Despite a low solubility product for most
of the natural and synthetic mineral samples, partial dissolution of
cations and anions affects the pH of the aqueous solution, which is
often rendered basic. Furthermore the dissolution is pH-dependent
and accounts for the buffer capacity of many mineral samples. The
situation becomes even more complex for composite minerals such
as barium titanate, where a dependence of the isoelectric point on
the solid contents in a BaTiO 3 particle dispersion was observed
(Paik and Hackley, 2000). It is therefore not surprising that the iso-
electric points reported for mineral samples cover a wide pH range
(Parks, 1965; Kosmulski et al., 2002).
While most of the early zeta potential results have been obtained
from the measurement of electrophoretic mobility, electrosonic
amplitude, and colloid vibration potential of mineral particle sus-
pensions, the streaming potential method was more recently
employed to study the surface charge of granular media and plate-
lets of single crystals. Lützenkirchen et al. (2010) investigated the
electrokinetic behavior of a sapphire single crystal which exhibits
an isoelectric point at a significantly lower pH than alumina powder.
Heberling et al. (2011) used the streaming potential method to
elucidate the reactivity of calcite in contact with water. Pecson et
al. (2012) coated silica sand with iron oxide to enhance the removal
of viruses. Laumann et al. (2013) used carbonate minerals for the
109
Applications
removal of nanoparticles for groundwater remediation. Deng et

al. (2014) revisited the selectivity of floatation processes for the
separation of sulphide and oxide minerals. They investigated the
effect of process water composition on the separation efficiency
by studying the interaction between mineral particles with solid
mineral surfaces.
Surface charge of carbonate and silicate sands
Natural minerals are commonly described in a simplified manner by

their average chemical composition. However, especially the sur-
face composition of such minerals deviates from the bulk chemistry.
Nevertheless, the streaming potential method offers a sensitive tool
to differentiate mineral samples according to their charging
behavior in an aqueous solution. Figure 8.12 shows the changes in
zeta potential with the composition of mixed silicate and carbonate
sands (Laumann et al., 2013). The correlation of the zeta potential
with the composition of the mixed sand samples deviates from
linearity, indicating the unequal contribution of silicate and
carbonate sands to the total surface charge. Since the zeta poten-
tial of heterogeneous samples is determined by the individual
sample surface areas, we assume a higher surface area for the
carbonate granular media.
Fig. 8.12.
Zeta potential of
mixed silicate and
carbonate sands.
The dotted line indi-
cates the expected
correlation of zeta
potential with mixed
sand composition
assuming a similar
surface area of
silicate and carbon-
ate granular media.
110
Tips and tricks
9. Tips and tricks

Despite its value for the analysis of the solid-liquid interface and its
manifold applications in material characterization, the zeta poten-
tial has been subject to much discussion in the past. The concerns
about the applicability and usefulness of zeta potential analyses
arose from unsatisfactory reproducibility and the occasional obser-
vation of peculiar effects that challenged the interpretation of the
obtained results.
In the minority of such cases, the electronics of the analytical

device for the streaming potential measurement was the reason for
any observed peculiarity. The majority of discrepancies between
expected and observed zeta potential results and the derived
information of the isoelectric point can either be explained by the
selection of an inappropriate sample holder or measuring cell or by
the parasitic contribution of measurement artefacts. This chapter
provides practical hints for a reliable solid surface zeta potential
analysis.
 9.1. Air bubbles
The solid sample is commonly mounted either in a dry state or after

storage in an aqueous solution in order to achieve equilibrium in
surface wetting or material swelling, or a complete soaking of the
material’s porous body. Before starting the streaming potential or
streaming current measurement, the capillaries of a porous sample
plug or the slit-shaped gap between samples with a planar surface
must be thoroughly filled with the aqueous electrolyte solution.
Auxiliary parameters such as the volume flow rate and the electrical
resistance are required to visualize the condition of the fluid inside
the capillary (gap). The significant drop in viscosity when air is
replaced by water makes the ratio between volume flow rate and
differential pressure, which corresponds to the permeability of the
capillary (gap), a sensitive parameter for monitoring this exchange.
111
Tips and tricks
However, small air bubbles that remain captured inside the

measuring cell, e.g. in hardly accessible corners or adhering to
hydrophobic material surfaces, are not detected by recording the
hydrodynamic flow. The electrical resistance becomes a substitute
for monitoring such air bubbles and their efficient removal, e.g. by
increasing the volume flow rate during an enhanced rinse process.
Besides the electrical resistance, air bubbles have an effect on the
initial slope of streaming current and streaming potential versus
differential pressure. Figure 9.1 illustrates the effect of air entrapped
in the proximity of a rectangular slit channel on the streaming
potential and streaming current of a polymer film. In the presence
of perturbing air inside the slit channel the initial streaming current
reads 0 nA, while the corresponding streaming potential measure-
ment indicates a strong polarization due to the high parasitic
electrical resistance.
Fig. 9.1.
Effect of air bubbles
entrapped inside the
measuring cell on
the initial values of
(a) streaming poten-
tial and (b) streaming
current for a
polymer film.
ζ Before starting the streaming potential / streaming current

measurement, the flow channel (capillary or slit-shaped
gap between flat samples) must be thoroughly filled with
the aqueous solution.
The electrical resistance can be used to monitor for small

air bubbles that remain captured inside the measuring cell.
112
Tips and tricks
 9.2. How does carbon dioxide affect the zeta potential?
The stability of a solid surface or surface coating in an aqueous

solution may be determined by the temporal change of the zeta
potential at the solid-liquid interface. In general, a decrease in
the negative zeta potential indicates an increasing surface hydro
philicity (see Figure 7.2). For natural fibers this behavior is inter-
preted in terms of fiber swelling (see Figure 7.4).
Figure 9.2 shows this swelling characteristic for a natural ligno

cellulosic fiber (Bismarck et al., 2002). After a fast initial decrease
the zeta potential approaches an equilibrium value. The experiment
shows the same effect for a polypropylene foil. Bismarck et al.
(1999) found similar behavior in poly(amide) and poly(ether ether
ketone) and interpreted this phenomenon in terms of swelling and
the removal of surface-adsorbed soluble components. For rigid
polymer films this behavior is more difficult to understand. This
chapter demonstrates that the adsorption of carbon dioxide (CO 2)
dissolved in the aqueous solution is responsible for this pheno
menon.
Fig. 9.2.
Time dependence
a natural fiber and a
polypropylene film.
113
Tips and tricks
Adsorption of carbon dioxide
The zeta potential of a poly(ethylene terephthalate) film shown in

Figure 9.3 was recorded for 70 min during a continuous nitrogen
purge (N 2, 99.95 vol%) of the aqueous 0.001 mol/l KCl solution.
The zeta potential hardly changes with time until the N 2 purge is
stopped. The negative zeta potential starts to decrease almost
instantaneously due to the immediate dissolution of CO 2 in the
aqueous electrolyte solution. As shown in Figure 9.3, this behavior
is remarkably reproducible.
Fig. 9.3.
Time dependence
of zeta potential
for a poly(ethylene
terephthalate) film
(PET).
Adsorption of CO 2 preferably occurs on hydrophobic surfaces

such as polymers. We may assume that CO 2 has a greater affinity
towards polymer surfaces than towards the surrounding water.
On the other hand the dissolution of CO 2 in water and the form

ation of carbonic acid shows its affinity towards the aqueous
solution. We may therefore interpret the decrease in the negative
zeta potential in terms of an increasing hydrophilicity of the
polymerCO 2 surface. The likely outcome is the acidification of
the polymer surface by adsorbed CO 2 , which is converted into
carbonic acid when in contact with water. The streaming potential
and streaming current method and thus the surface zeta potential
analysis are extremely sensitive to the outermost surface chemis-
try and its changes at very low concentration of adsorbates (at a
solute concentration in the ppb range). The surface acidification
114
Tips and tricks
effect observed by the zeta potential is thus not detected by the

pH measurement in the bulk aqueous solution (however, the pH
starts to decrease with the onset of CO 2 dissolution after stopping
the N 2 purge until dissolution equilibrium is obtained, leading to pH
5.5).
Carbonate adsorption
When starting the pH titration in the alkaline range, a pronounced

“hump” in the titration curve may be observed around pH 6. The
point of inflection at pH 6.5 coincides with the pK value for the
equilibrium
This phenomenon disappears when titration starts at neutral con

dition, as shown for a glass surface in Figure 9.4a. We conclude
that carbonate (CO 32–) is chemically captured in the measuring
electrolyte at a high pH and gets adsorbed on the solid surface. By
preventing CO 2 dissolution in the aqueous electrolyte solution by
an N 2 purge and starting the pH titration in the alkaline range, the
titration curve indicates the dissociation of acidic silanol groups
only (Figure 9.4b).
Fig. 9.4.
pH dependence of
zeta potential for a
borosilicate glass
surface.
(a) Comparison of
titration from high
and neutral pH
without N2 purge.
(b) Titration from
a high pH with N2
purge.
115
Tips and tricks
When is it necessary to purge with nitrogen?
The sensitivity of solid surfaces towards adsorption of CO2, which

dissolves in the aqueous electrolyte solution, is high for hydro
phobic materials such as polymers but also for gold or quartz sur-
faces, especially at small surface areas.
In practice, the prevention of CO 2 dissolution by purging the

aqueous solution with N 2 is highly recommended
• for the zeta potential analysis of hydrophobic material samples

with planar surfaces,
• for a pH titration starting at an alkaline pH,
• for an investigation of the time dependence of zeta potential at
a given electrolyte composition (i.e. at a fixed pH).
Figure 9.5 shows the time dependence of the zeta potential for
poly(phenylene sulfide), PPS, at different electrolyte pH. A repeat-
ability of the zeta potential of 1 % is obtained for a time period of
80 min.
Fig. 9.5.
Time dependence
of zeta potential
for poly(phenylene
sulfide), PPS, at
different electrolyte
pH with N2 purge.
116
Tips and tricks
An N 2 purge is not necessarily required
• for the zeta potential analysis of hydrophilic material samples

(high surface concentration of functional groups) with planar
surfaces,
• for a pH titration starting at a neutral pH and proceeding
towards either an acidic or an alkaline pH,
• for the zeta potential analysis of material samples with a large
surface area such as fibers and granular media.
Despite the influence of dissolved CO 2 that dominates the time

dependence of the zeta potential, a reproducible measurement
for a hydrophobic material with a small surface area may even be
maintained without a continuous purge with N 2. Figure 9.6 shows
a repetitive analysis of the pH dependence of the zeta potential for
a polypropylene film without N 2 purge. We obtain
• an average standard deviation of (1.7 ± 0.4) mV

• an IEP at pH 3.87 ± 0.08.
In order to achieve such reproducibility, it is important to maintain

the same measurement procedure.
Fig. 9.6.
pH dependence of
zeta potential for a
polypropylene film
without N2 purge.
117
Tips and tricks
ζ In practice, CO 2 from air might have a severe impact on

solid surface zeta potential analysis.
• On the one hand, adsorption of CO2 preferably occurs

on hydrophobic surfaces such as polymers.
• On the other hand, CO 2 is chemically captured
(especially at a high pH) and adsorbed as carbonate
ions on the solid surface.
Both effects are prevented by purging the aqueous

solution with N 2.
 9.3. Asymmetric sample mounting
The non-destructive zeta potential analysis of large and/or rigid

materials requires the clamping cell approach for sample mounting
described in chapter 5.1. In this experimental approach the use of
a reference sample and thus the contribution of its interfacial
charge to the overall zeta potential are indispensable. By assuming
an equal contribution of the material and reference samples to the
zeta potential ζ measured and by knowing the zeta potential ζ reference of
the reference surface, the material surface zeta potential ζmaterial may
be calculated according to
Eq. 9.1
Walker et al. (2002) introduced a more general formula for a

heterogeneous sample packing of granular media composed of
two different materials,
118
Tips and tricks
Eq. 9.2
where X is the fraction of the surface area of sample 1.
An example for a binary mixture of granular sands with different

chemistry, silicate and carbonate, is shown in Figure 8.12. The
zeta potential is determined for a series of different weight compo-
sitions. The dotted line shows the average zeta potential assuming
the same surface area (X = 0.5 in Eq. 9.2). The best fit, however,
indicates a higher contribution of carbonate sand than derived from
the weight concentration.
Eq. 9.2 may be converted for the analysis of planar samples with a
significantly different roughness between the material and reference
surfaces,
Eq. 9.3
The fractional contribution of the surface area of material and

reference surfaces is hardly known. The average zeta poten-
tial determined by an asymmetric arrangement of the sample in
a clamping cell thus becomes representative for the interfacial
behavior of the material surface. Provided that the same type of
reference sample is always used, surface modification and treat-
ment processes applied to a certain material can be studied with
the same quality as for a symmetric sample mounting.
119
Tips and tricks
ζ The non-destructive zeta potential analysis of large and/

or rigid materials requires a clamping cell and the use of a
reference sample, whose interfacial charge contributes to
the overall measured zeta potential.
When using the same type of reference sample, an

asymmetric arrangement delivers the same quality
of information on surface modification and treatment
processes as a symmetric sample mounting.
120
Outlook
10. Outlook
A combination of streaming potential and streaming current
measurem ents enables the assessment of the electrokinetic effect
of interfacial conductance besides the solid surface zeta poten-
tial (Zimmermann et al., 2001). Knowledge of the conductance
and thus the ion distribution in the solid-liquid interfacial region
reveals in-depth information about the surface charge as well as
the structure of the solid surface. Effects of porosity or surface and
bulk material swelling have already been discussed in chapters 6.5
and 6.10, respectively. Recently, advanced electrokinetic studies
have been employed successfully to characterize hydrogel films
(Zimmermann et al., 2013).
Another development of the streaming potential method focuses on

zeta potential analysis under conditions of high salinity. While the
approach of extrapolating the zeta potential, which is obtained at
lower ionic strength, was suggested in chapter 6.2, Vinogradov et
al. (2010) have published reasonable data in an aqueous solution
of > 0.4 mol/l NaCl. Their findings question the validity of the model
of the electrochemical double layer and the conclusions derived
therefrom.
The analysis of the zeta potential at metal-water interfaces may

hold great interest since it is expected to contain important infor-
mation for the understanding of corrosion processes. The likely
activation of electrochemical processes at the metal surface by the
streaming potential and the streaming current and the interference
of the metal sample with the measuring electrodes still prohibit a
successful application of the solid surface zeta potential. Further
improvement of measuring devices and a deeper understanding of
contributing interfacial processes are thus required to extend the
zeta potential analysis to a meaningful characterization of metal
surfaces.
Last but not least, a variety of samples of rather complex shape or

large size demand a non-destructive analysis of the solid surface
121
Outlook
zeta potential. Appropriate sample holders and measuring cells

or even a modification of existing devices for streaming potential
and streaming current measurements are required to meet this
challenge.
All in all, it is evident that both the fields of application and the
instrumental tools leave enough space for further exploration of the
solid surface zeta potential.
122
References
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The ZETA Guide

Principles of the streaming potential technique

A practical guide to streaming

All rights reserved. No part of this publication may be

Published by Anton Paar GmbH. Printed in Austria.

Anton Paar GmbH

Date: March 2014

Specifications subject to change without notice. | A48IP010EN-A

Graz, March 2014  Thomas Luxbacher

3. The zeta potential 12

3.1. Surface charge formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4. The streaming potential technique 20

4.1. Zeta potential calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

5.1. Measuring cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

6. Dependences of the zeta potential 42

7.1. Zeta potential. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

8.1. Membranes and filters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

9. Tips and tricks 111

9.1. Air bubbles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

10. Outlook 121

11. References 123

Why is the zeta potential relevant? In particle suspensions and

about surface functionality (carried by chemical groups that inter-

Which knowledge is required to read zeta potential results

After a brief review of the historical development of the zeta poten-

The development of an appropriate model was essential for the

G. H. Quincke H. v. Helmholtz M. v. Smoluchowski

For more detailed information about the history of electrokinetics

3. The zeta potential

In contact with an aqueous solution, a solid surface assumes a

This so-called Stern model of the EDL may be extended by a sub-

Eq. 3.1 relates the zeta potential ζ to the electrokinetic charge

ε 0 is the vacuum permittivity, ε r is the dielectric coefficient of the

ζ The zeta potential is a parameter which describes the

The model of the electrochemical double layer defines

 3.1. Surface charge formation

The surface charge at the interface between a solid material and an

• acid-base reactions between surface functional groups and an

Among these dominant contributions to the surface charge, an

Charge formation by reaction of surface functional groups

Figure 3.2 schematically shows the interaction of acidic and basic

Acidic groups such as carboxylic acid, sulfonic acid or hydroxyl

The equilibrium of the surface charging process depends on

Charge formation by adsorption

For surfaces without functional groups we also find a zeta poten-

There is still a debate in the scientific world about how to explain

The other model explains the charging behavior at a hydrophobic

Be it ion replacement or water molecule polarization, the effect on

ζ The surface charge at the interface between a solid

Due to preferable adsorption of hydroxide ions, hydro­

 3.2. Electrokinetic phenomena

The zeta potential is a model parameter that describes the charging

In general, an electrokinetic effect is observed at an interface

Electricity causes movement

Electrophoretic mobility, electro-osmotic flow and electrokinetic

A direct current (dc) field is used to motivate charged colloidal solid

The same dc field provokes liquid motion through a porous solid

The electrokinetic sonic amplitude (ESA) is the ultrasound

Movement causes electricity

Sedimentation potential, streaming potential and colloid vibra-

a potential difference. When using a centrifuge, the separation

The streaming potential is generated by the tangential flow of

ζ The zeta potential is determined by the measurement of

Graz, March 2014 Thomas Luxbacher

Due to preferable adsorption of hydroxide ions, hydro

For other sources of conductance, i.e., electronic or ionic con