THE EFFECT OF pH AND ELECTROLYTE

CONCENTRATION ON THE DISPERSION

PROPERTIES OF TITANIUM DIOXIDE
Jan Gustafsson

Department of Physical Chemistry

bo Akademi University
bo, Finland
2003

To Josi & Matias

Imagine a man
Where it all began
A scientist pacing the floor
In each nation - always eager to explore
To build the best big stick
To turn the winning trick
But this was something more...
-Neil Peart, Rush

ii

TABLE OF CONTENTS:
LIST OF PUBLICATIONS
CONTRIBUTION OF THE AUTHOR
ABSTRACT
1. INTRODUCTION .......................................................................................................1
2. OUTLINE OF THE STUDY ......................................................................................2
3. INTERACTION FORCES .........................................................................................3
3.1 ATTRACTIVE FORCES ................................................................................................. 4
3.2 THE ELECTRICAL DOUBLE LAYER .............................................................................. 5
3.3 THE ZETA POTENTIAL ................................................................................................ 7
3.4 INFLUENCE OF PH AND ELECTROLYTE ON THE ZETA POTENTIAL ................................. 9
3.5 REPULSIVE FORCES .................................................................................................. 12
3.6 THE TOTAL ENERGY OF INTERACTION (THE DLVO THEORY) ..................................... 12
4. RHEOLOGY..............................................................................................................13
4.1 VISCOSITY ............................................................................................................... 14
4.2 NON-NEWTONIAN FLOW PROPERTIES ....................................................................... 14
4.3 THE SHEAR YIELD STRESS ........................................................................................ 15
4.4 CORRELATION TO PARTICLE INTERACTION............................................................... 16
5. SEDIMENTATION...................................................................................................18
5.1 SEDIMENTATION VELOCITY AND PARTICLE SIZE....................................................... 18
5.2 CONSOLIDATION ...................................................................................................... 19
5.3 COMPRESSIVE YIELD STRESS ................................................................................... 20
5.4 CORRELATION TO PARTICLE INTERACTION............................................................... 20
6. MATERIALS .............................................................................................................21
7. EXPERIMENTAL METHODOLOGY ..................................................................22
7.1 ELECTROACOUSTIC MEASUREMENTS ....................................................................... 22
7.2 RHEOLOGICAL MEASUREMENTS .............................................................................. 24
7.3 SEDIMENTATION MEASUREMENTS ........................................................................... 26
8. RESULTS AND DISCUSSION................................................................................28
8.1 THE RELATIONSHIP BETWEEN ZETA POTENTIAL AND RHEOLOGY .............................. 28
8.1.1 Monovalent electrolytes ...................................................................................28
8.1.2 Divalent electrolytes ........................................................................................33
8.2 THE YIELD STRESS (THE STRESS OVERSHOOT).......................................................... 36
8.3 SEDIMENTATION AND CONSOLIDATION .................................................................... 40
8.3.1 The effect of initial solids content ....................................................................40
8.3.2 The effect of electrolyte concentration.............................................................44

iii

9. CONCLUSIONS........................................................................................................48
10. SUGGESTIONS FOR FUTURE WORK..............................................................51
11. ACKNOWLEDGEMENTS ....................................................................................52
12. REFERENCES ........................................................................................................53
APPENDIX (ARTICLES I VI)

iv

List of publications
The thesis is based on the following articles that are referred to in the text by their Roman
numerals.
I
The Influence of pH and NaCl on the Zeta potential and Rheology of Anatase
Dispersions.
J. Gustafsson, P. Mikkola, M. Jokinen and J. B. Rosenholm.
Colloids and Surfaces A, 175 (2000) 349-359.
II
Correlation between the Zeta Potential and Rheological Properties of
Anatase Dispersions.
M. Kosmulski, J. Gustafsson, and J. B. Rosenholm.
Journal of Colloid and Interface Science, 209 (1999) 200-206.
Erratum: Journal of Colloid and Interface Science, 233 (2001) 367-368.
III
Ion Specificity and Viscosity of Rutile Dispersions.
M. Kosmulski, J. Gustafsson, and J. B. Rosenholm.
Colloid and Polymer Science, 277 (1999) 550-556.
IV
Shear-Induced Aggregation of Anatase Dispersions Investigated by
Oscillation and Low Shear Rate Viscometry.
J. Gustafsson, E. Nordenswan, and J. B. Rosenholm.
Journal of Colloid and Interface Science, 242 (2001) 82-89.
V
Effect of pH on the Sedimentation, potential, and Rheology of Anatase
Suspensions.
J. Gustafsson, E. Nordenswan, and J. B. Rosenholm.
Colloids and Surfaces A, 212 (2003) 235-247.
VI
Consolidation behaviour in Sedimentation of TiO2 Suspensions in the
presence of Electrolytes.
J. Gustafsson, E. Nordenswan, and J. B. Rosenholm.
Journal of Colloid and Interface Science, (2003) accepted for publication.

Supporting publication
VII
Charge Interactions in Semi-Concentrated Titania Suspensions at Very High
Ionic Strengths.
M. Kosmulski, S. Durand-Vidal, J. Gustafsson, and J. B. Rosenholm.
Colloids and Surfaces A, 157 (1999), 245-259.

Contribution of the author

The experimental work included in this thesis (I - VI) has been performed by the author
with the following exceptions.

The experimental work of articles II and III was done in collaboration with Marek
Kosmulski.

The author has been chiefly in charge of the preparation of articles I, IV, V and VI, and
parts of articles II and III.

vi

Abstract
Dispersions (mixtures) of colloidal particles in aqueous solutions at high solids
concentrations are found in various industrial processes, such as ceramic processing,
paints and cosmetics. Many of the dispersion properties, for example the mechanical
strength, the elastic and flow behaviour and the rate of settling of the particles, are
determined by the interactions between the particles. Therefore they have a significant
effect on the process duration and the quality of the final product. By changing the
interactions, the dispersion properties may be controlled. This may be done by
addition of for example electrolytes, polymers or surfactants and/or by changing the
pH.
In this thesis the rheological (flow) and the consolidation (particle packing by
sedimentation) behaviour of concentrated dispersions of TiO2 were studied at different
physico-chemical conditions. The interaction between the particles was modified by
altering the zeta potential, which was used as a measure of the electrostatic repulsion.
The zeta potential was changed by adjusting the pH of the solution or by addition of
salt. The electrolyte (salt) concentrations were varied over a wide range. TiO2 particles
of both anatase and rutile were evaluated. 1:1 and 2:1 electrolytes were investigated.
A not so commonly recognized flow phenomenon of particle dispersions, the stress
overshoot at the onset of shear, was used as an indication of the yield stress. The
stress overshoot phenomenon was characterized further at various shear rates and at
different interaction properties.
The origin of the stress overshoot was concluded to be a balance between the build-up
and breakdown of a shear-induced structure in the dispersion. The pHiep (pH of zero
zeta potential) of TiO2 was found to shift towards higher pH with increasing
electrolyte concentration. The maximum yield stress at the vicinity of the pHiep was
also found to shift towards higher pH with increasing electrolyte concentration, which
supported the zeta potential measurements. Furthermore, an asymmetry around the
pHiep was observed in the consolidation process, a phenomenon that was related to the
difference between the an- and cation in the electrolyte. In turn, this difference
between the ion pair resulted in the observed shifts of both the pHiep and the maximum
yield stress.

vii