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APCBEE Procedia 9 (2014) 13 – 17

ICBEE 2013: September 14-15, New Delhi, India

Particle size and Zeta Potential of ZnO

Roman Marsalek
Department of Chemistry, Faculty of Science, University of Ostrava, 30. Dubna 22, Ostrava, 701 03, Czech republic

Abstract

The influence of dispersant, pH and various additives on stability of ZnO suspension have been studied. Water and
ethylene glycol were used as dispersants, sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and
sodium carboxymethyl cellulose (NaCMC) have been adsorbed on ZnO particles. Equilibrium in the system is mostly
influenced by pH. The lowest stability of suspensions of ZnO was found around isoelectric point which was confirmed by
simultaneous measurement of particle size and zeta potential. The values of the zeta potential were also affected by the
presence of surfactants, especially SDS and CTAB.

© 2013Roman
© 2014 Published by Elsevier
Marsalek. PublishedB.V. Selection
by Elsevier B.V. and/or peer review under responsibility of Asia-Pacific
Chemical,
Selection andBiological
peer review & Environmental
under Engineering
responsibility of Society Biological & Environmental Engineering Society
Asia-Pacific Chemical,

Keywords: ZINC OXIDE, PARTICLE SIZE DISTRIBUTION, ZETA POTENTIAL

1. Introduction

Zinc oxide (ZnO) has generated considerable attention because of its optical, magnetic, antibacterial and
semiconducting properties. Its nanostructures exhibit interesting properties: high catalytic efficiency and
strong adsorption capacity. This is extensively used in many applications such as cosmetics, paints, ceramics
and electronics [1], [2]. Recently, much effort has been devoted to study ZnO as a very promising
photocatalyst for photocatalytic degradation of water pollutants, owing to its high activity, low cost and
environmental friendly feature. Some problems still remain to be solved in its application, such as degraded
photocatalytic activity in aqueous solution introducing acid or base [3]. Zinc oxide is an important
semiconductor suitable for a wide range of applications due to its unique electronic and optical properties.

Corresponding author. Tel.: +0-420-597-092-192; fax: +0-420-596-120-478.
E-mail address: roman.marsalek@osu.cz

2212-6708 © 2014 Roman Marsalek. Published by Elsevier B.V.

Selection and peer review under responsibility of Asia-Pacific Chemical, Biological & Environmental Engineering Society
doi:10.1016/j.apcbee.2014.01.003
14 Roman Marsalek / APCBEE Procedia 9 (2014) 13 – 17

ZnO is used in optical and photonic crystals, sensors, colloidal lithography, and catalyst support [4]. Great
variety of colloid chemical methods and physical techniques are being used to synthesize zinc oxide particles
with controlled size [5]. In pharmaceutical suspensions, when a solid active ingredient is dispersed in a liquid,
the problems are related to agglomeration, flocculation (increase of particle size) and sedimentation: because
of their high surface area, micro or nanoparticles form aggregates or agglomerates due to Van der Waals or
other attractive forces [1]. Monitoring the presence of nanoparticles in dispersions having broad particle size
distributions can be a problem for many measurement techniques because large particles or even aggregates
of the smaller particles can mask the presence of the sought after nanoparticles [6].
There are many ways to affect the stability of suspensions of nanoparticles. It is reported that particle
surface coating is one of the effective way to improve their stability and agglomeration condition [8]. Also pH
is an important parameter for controlling the particle sizes of colloids because it affects the stability of surface
charge and particle interactions [7]. The stability of suspensions can be further influenced by the addition of
surfactants. The cationic surfactant (CTAB) exhibits adsorption on ZnO due to electrostatic attraction between
the negative surface and positively charged surfactant. In the ZnO case, a small concentration of anionic
surfactant causes a decrease of suspension stability. Fine oxide particles are aggregated by the presence of
surfactants as a result of a strong hydrophobic interaction after adsorption [9]. Similar results were also
observed in the interaction of cationic and anionic surfactants on clays and coals. [10]-[13]. The presence of
surfactants in the synthesis of nano zinc oxide also affects the shape of the particles. ZnO nanostructures were
synthesized by hydrothermal method using different molar ratios of cetyltrimethylammonium bromide
(CTAB) and Sodium dodecyl sulfate (SDS) as structure directing agents. The results indicate that the mixture
of cationic-anionic surfactants can significantly modify the shape and size of ZnO particles. Various
structures such as flakes, sheets, rods, spheres, flowers and triangular-like particles sized from micro to nano
were obtained. Recently, there have been lots of works on the synthesis of ZnO nanostructures using different
surfactants like ethylenediaminetetraacetic acid (EDTA), sodium dodecyl sulfate (SDS),
cetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG) and polyethyleneimine (PEI) [2]. To
improve the stability of suspensions are also used polymers. The suspensions were formulated with ZnO at a
fixed concentration (5 wt%), sodium poly-(acrylate), as a viscosifier, and sodium dodecylsulfate (SDS), as a
wetting agent. Polymer adsorption serves as an effective way for modifying particle surface and hence
improving the stability of pharmaceutical suspensions against flocculation [1].
The main purpose of sample preparation is to break up flocs and disperse the particles. This is achieved by
increasing the surface charge of the particles and zeta potential measurements allow optimization of this
procedure. The value of the zeta potential indicates possible behavior of the dispersion. Particles which have
got the zeta potential between minus 30 to plus 30 mV show tendency to the coagulation. This fact is the most
expressive at the isoelectric point, when the zeta potential equals zero mV. The isoelectric points (IEPs) of
ZnO were found around at pH 8.0 [7], 9.7 [14], 9.8 [3], 10.3 [8]. Zeta potential is possible to affect in various
ways also in the case of ZnO. After modification, the nanoparticles of ZnO/SiO 2 were negatively charged over
the whole pH value range examined [3]. In case of both series the zeta potential values of the samples
increased with increasing indium ion content. It can be explained by the presence of indium ions on the
surface of the crystals, due to their specific adsorption in the electric double layer [5]. It was obvious that the
pH dependence of zeta potentials for ZnO nanoparticles shifted completely to that for TiO 2 nanoparticles after
TiO2 coating, also confirming the formation of core-shell structure [14]. The pH in isoelectric point was 10.3
for ZnO without coating, but it shifted to 6.0 for coated ZnO. The change of pH in isoelectric point would
attribute to the highly monodisperse condition for ZnO nanoparticles coated with Al 2O3 [8]. Zeta potential
measurements indicated that addition of the cationic surfactant caused a positive increase of the zeta potential
[9], [11]-[13]. The combined effect of the pH of a medium and the addition of commercial additives on the
zeta potential and particle radius of aqueous suspensions zinc oxide was studied in this work.
 Roman Marsalek / APCBEE Procedia 9 (2014) 13 – 17 15

2. Experimental

2.1. Materials

We used ZnO powders from different manufacturers to prepare 1 wt.% dispersions (stock dispersions),
each dispersed in water (or ethylene glycol). All samples were sonicated (5 minutes) to make them
homogeneous. Sodium dodecyl sulfate (SDS, Sigma-Aldrich), cetyltrimethylammonium bromide (CTAB,
Sigma-Aldrich) and sodium carboxymethyl cellulose (NaCMC) of analytical reagent grade were used for
stabilization of the suspensions. Hydrochloric acid (HCl, Sigma-Aldrich) and sodium hydroxide (NaOH,
Sigma-Aldrich) were used for adjusting the pH during zeta potential measurements. In addition, particle size
distribution was also measured in ethylene glycol (EG, Sigma-Aldrich).

2.2. Methods

2.2.1. Particle size distribution

For dynamic light scattering measurements 12 mm cell (DTS 0012) was used. One milliliter of distilled
water (or ethylene glycol) was added to the cell and then 50 μl from stock dispersions were added. Samples
were again sonicated for 5 minutes. Size distributions of the nanoparticles were determined with a Malvern
Zetasizer Nano ZS (Malvern Instruments Ltd., GB) by the DLS technique. The suitable parameters (viscosity,
absorption and refractive index) were chosen for each ZnO and dispersants. For ZnO sample: absorption 0.1,
refractive index 2.0, for water: viscosity 1.0031cP, refractive index 1.33, for ethylene glycol viscosity 1.98 cP,
refractive index 1.44. The pH value of each suspension was adjusted by adding either NaOH or HCl.
Histograms with the distributions of sizes were recorded.

2.2.2. Zeta potential measurements

The zeta potential was measured by analyzing 0.1 g of ZnO in 10 ml of water (or additives solutions) using
the Zetasizer Nano ZS (Malvern Instruments Ltd., GB). Before zeta potential measurements all samples were
sonicated for 5 minutes. Zetasizer Nano ZS uses Laser Doppler Velocimetry to determine electrophoretic
mobility. The zeta potential was obtained from the electrophoretic mobility by the Smoluchowski equation.
The dynamic method consisted of using ZS Malvern Zetasizer device coupled with an automatic titrator
(Malvern MPT-2). pH of the suspensions was automatically adjusted by this automatic titrator using
hydrochlorid acid (0.25 and 0.025 mol/l) and sodium hydroxide (0.25 mol/l). Concentrations of additives
(SDS, CTAB, NaCMC) were 5mmol/l.

Fig. 1. Size distribution of ZnO by number. Dispersants: water (red line), ethylene glycol (green line)
16 Roman Marsalek / APCBEE Procedia 9 (2014) 13 – 17

3. Results and Discussion

3.1. Particle size distribution

Particle size distribution (and also coagulation) can be influenced in several ways: sonification , adding a
stabilizer (e.g. sodium hexametaphosphate hexamethyl) [6]. Dispersant also plays very important role. The
following picture shows the difference in the particle size distribution of ZnO in water and in ethylene glycol.
The picture shows great differences in the particle size distribution. The value of Z-average was 735nm for
water and 340 nm in ethylene glycol, parameter Number mean was 151nm for water and 49 nm for ethylene
glycol, respectively. It was the same sample of ZnO. The probable cause of the difference is much higher
viscosity of ethylene glycol compared to water (20 times higher). In the ethylene glycol the particles of ZnO
get to each other more difficultly and rate of coagulation is lower. From this point of view, selecting the
proper dispersant and setting methodology for measuring is very important.

3.2. The zeta potential

Fig. 2. (a) The influence of pH on the zeta potential (circles) and size (triangles) of ZnO particles. (b) The influence of additives on the
zeta potential of ZnO particles from pH 7 to pH 12.

The picture 2(a) shows the changes of the zeta potential during NaOH titration. In addition particle size of
our sample was followed. When we started titration, the pH was 7.3, the value of the zeta potential + 35 mV
and diameter size approximately 50 nm. Addition of NaOH caused decrease of the zeta potential and increase
of particle size. The maximum size was found at pH 10.2 near to the isoelectric point. In other words, for ZnO
suspensions it is necessary to know pH, adjust it and keep it at a value which the system is stable at. After the
addition of SDS, CTAB and NaCMC, ions were adsorbed and caused a change to the zeta potential (picture
2b). In the case of adsorption of CTAB the zeta potential increased. In contrast, in the case of adsorption of
SDS and NaCMC the zeta potential was shifted into negative values. The new values of IEP were: pH 11 in
case of CTAB, pH 9.4 in case of NaCMC and pH 8.9 when we added SDS. With the help of additives, we are
able to change the zeta potential of suspensions of ZnO and thus affect the stability of suspensions. Adding a
cationic surfactant extended stable region (zeta potential above |30mV| ) around neutral pH. Addition of
anionic surfactant extended stable region in strongly alkaline pH. Adding NaCMC did not significantly affect
the stability of ZnO suspension.
 Roman Marsalek / APCBEE Procedia 9 (2014) 13 – 17 17

4. Conclusions

Stability of suspensions of ZnO can be influenced by a variety of ways. Coagulated particles are influenced
by the type of dispersant, pH and/or the presence of other substances. The stability of suspensions can be
monitored by measuring the zeta potential. Suspensions of ZnO are stable in the neutral pH range.
Suspensions are also more stable in the ethylene glycol with comparison with water. At a certain pH range it
is also possible to create stable suspensions by adding surfactants, namely SDS and CTAB.

Acknowledgements

Article has been done in connection with project Institute of environmental technologies, reg. no.
CZ.1.05/2.1.00/03.0100 supported by Research and Development for Innovations Operational Programme
financed by Structural Founds of European Union and from the means of state budget of the Czech Republic.

References

[1] Chabni M., Bougherra H., Lounici H., Ahmed-Zaïd T, Canselier J-P, Bertrand J. Evaluation of the Physical Stability of Zinc
Oxide Suspensions Containing Sodium Poly-(acrylate) and Sodium Dodecylsulfate. J. Dispersion Sci. Technol. 2011; 32: 1786-1798.
[2] Ramimoghadam D., Hussein MZB., Taufiq-Yap YH. The Effect of Sodium Dodecyl Sulfate (SDS) and
Cetyltrimethylammonium Bromide (CTAB) on the Properties of ZnO Synthesized by Hydrothermal Method. Int. J. Mol. Sci. 2012;
13:13275-13293.
[3] Zhai J., Tao X., Pu Y., Zeng XF, Chen JF. Core/shell structured ZnO/SiO 2 nanoparticles: Preparation, characterization and
photocatalytic property. Appl. Surf. Sci. 2010; 257: 393–397.
[4] Boz I, Kaluza S, Borog˘lu MS, Muhler M. Synthesis of high surface area ZnO powder by continuous precipitation. Mater. Res.
Bull. 2012; 47:1185–1190.
[5] Pál E., Hornok V., Oszkó A., Dékány I. Hydrothermal synthesis of prism-like and flower-like ZnO and indium-doped ZnO
structures. Colloids Surf., A 2009; 340:1–9.
[6] Dukhin AS., Goetz PJ., Fang X., Somasundaran P.. Monitoring nanoparticles in the presence of larger particles in liquids using
acoustics and electron microscopy. J. Colloid Interface Sci. 2010; 342:18–25.
[7] Tso Ch., Zhung Ch., Shih Y., Tseng YM., Wu S., Doong R. Stability of metal oxide nanoparticles in aqueous solutions. Water
Sci. Technol. 2010; 61:127-133.
[8] Yuan F., Peng H., Yin Y., Chunlei Y., Ryu H. Preparation of zinc oxide nanoparticles coated with homogeneous Al2O3 layer.
Mater. Sci. Eng., B 2005; 122:55–60.
[9] Sadowski Z., Polowczyk I. Agglomerate flotation of fine oxide particles. Int. J. Miner. Process. 2004; 74:85– 90.
[10] Marsalek R., Taraba B. Adsorption of SDS on coal. Prog. Colloid Polym. Sci. 2008; 135:163-168.
[11] Marsalek R. The influence of surfactants on the zeta potential of coals. Energy Sources, Part A. 2009; 31: 66-75.
[12] Marsalek R., Navratilova Z. Comparative study of CTAB adsorption on bituminous coal and clay mineral. Chem Pap. 2011; 65:
77-84.
[13] Marsalek R., Taraba B. The influence of temperature on the adsorption of CTAB on coals. Colloids Surf., A 2011; 383: 80-85.
[14] Liao MH., Hsu ChH., Chen DH. Preparation and properties of amorphous titania-coated zinc oxide nanoparticles. J. Solid State
Chem. 2006; 179:2020–2026.