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Point of Zero Charge and Isoelectric Point of Alumina

Article in Materials and Manufacturing Processes · July 2008

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Point of Zero Charge and Isoelectric Point of Alumina
Jelena J. Gulicovski a; Ljiljana S. Čerović a; Slobodan K. Milonjić a
a
The Vin a Institute of Nuclear Sciences, Belgrade, Serbia

Online Publication Date: 01 July 2008

To cite this Article: Gulicovski, Jelena J., Čerović, Ljiljana S. and Milonjić,
Slobodan K. (2008) 'Point of Zero Charge and Isoelectric Point of Alumina',
Materials and Manufacturing Processes, 23:6, 615 — 619
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 Materials and Manufacturing Processes, 23: 615–619, 2008
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DOI: 10.1080/10426910802160668
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Point of Zero Charge and Isoelectric Point of Alumina

Jelena J. Gulicovski, Ljiljana S. Čerović, and Slobodan K. Milonjić

The Vinča Institute of Nuclear Sciences, Belgrade, Serbia

The point of zero charge, pHpzc , and the isoelectric point, pHiep , of a commercial alumina sample was investigated in KNO3 solutions.
The influence of the concentration and the initial pH value of KNO3 solution used for preparation and equilibration of the alumina suspension, as
well as of the alumina/solution ratio on pHpzc and pHiep were investigated. The obtained results indicate that pHiep values are dependent on initial
pH values of KNO3 solutions used for equilibration of alumina suspensions. Simultaneously with isoelectric point determination, the particle size
of alumina was also measured. It was shown that the particle size of alumina increases with increasing suspension pH due to agglomeration,
reaching the maximum value at pHiep .

Keywords Alumina; Interface; Isoelectric point; Point of zero charge; Surface properties.

Introduction
Since the pH dependent surface charging of aqueous
metal oxide dispersions is a very important field of research,
determination of their point of zero charge (pHpzc ) and
isoelectric point (pHiep ) becomes necessary. These terms are
used to define the state of the surface of a dispersed solid
phase at a solid-electrolyte solution interface. The point of
zero charge is the pH value where negative ([MO− ]) and
positive ([MOH+ 2 ]) surface concentrations are equal, i.e.,
surface charge,
0 = 0. The surface charge is negative at
pH > pHpzc and positive at pH < pHpzc . The isoelectric point
is the pH at which zeta potential of a molecule or surface is
equal to zero,  = 0. In order to get a sharp isoelectric point,
the molecule (or surface) must be amphoteric, meaning it
must have both acidic and basic functional groups. In the
simplest case, if the specific sorption of ions and dissociation
of counterions and neglected, then pHpzc coincides with
pHiep . It is known that pHpzc (and also pHiep ) of solids
depends on the synthesis process, stoichiometry, crystal
structure, degree of surface hydration, and the presence of
impurities.
The pHpzc and pHiep values for various aluminium oxides,
hydroxides, as well as related materials, reported in literature,
vary widely (from pH = 5 to pH = 96). Collections of
these values can be found in the Parks and Kosmulski review
articles [1–5].
Bearing in mind such discrepancies in pHpzc and
pHiep , obtained by various authors, even for the same
kind of alumina, our aim was to make a detailed study
of the influence of experimental protocol (electrolyte
concentration, alumina/solution ratio, and equilibration pH
of alumina suspension) on pHpzc and pHiep .
Received January 28, 2008; Accepted March 14, 2008
Address correspondence to Slobodan K. Milonjić, The Vinča Institute
of Nuclear Sciences, P.O. Box 522, Belgrade 11001, Serbia; E-mail:
smiloni@vin.bg.ac.yu
615
Experimental
As a model, high purity -alumina powder (AKP-30,
Sumitomo, Japan) was chosen in this study. The powder
had the following characteristics: 99.99% -Al2 O3 ,
mean particle diameter d50 = 032 m, specific surface area
Sp = 5–10 7 m2 g−1 , and density 3.97 g cm−3 . According
to the producer, impurities included 8 ppm Si, 2 ppm Na,
2 ppm Mg, 1 ppm Cu, and 5 ppm Fe.
The point of zero charge of the alumina powder was
determined by the batch equilibration method [6], using
KNO3 (0.001–0.1 mol l−1 ) as a background electrolyte,
whose initial pH values were adjusted by small additions
of diluted (0.1 mol l−1 ) nitric acid or potassium hydroxide.
This method aimed at determination of an exact PZC value,
diminishes the influence of soluble species, and as such it
is advantageous over the potentiometric titration method.
This influence is eliminated by applying separate probes at
different pH values, ranging from low to high ones. It is
known that the solubility of the solid material reaches its
minimum at PZC, increasing towards lower and higher pH
values. In the middle region of pH, where the plateau is
registered, the quantity of soluble species is the smallest,
thus having a negligible influence on the PZC. We have
shown [7–9] that the potentiometric titration method can
give much higher PZC values for oxides/solid of significant
solubility. This is especially pronounced if the titration starts
at pH values, which are either very low or very high in
respect to PZC, i.e., at pH values where the solubility of the
examined material is appreciable. The ionic species formed
by dissolution will, as the titration goes on, absorb H+ or
OH− ions (in regard to the titration region) leading to an
incorrect PZC value. It happens sometimes that the formed
hydrolytic species are sorbed on the powder surface. In that
case, the determination of PZC value corresponds to one
of such species. For that reason, we have used the batch
equilibration method for PZC determination.
A Zetasizer Nano with 633 nm He-Ne laser equipped
with an MPT-2 Autotitrator manufactured by Malvern
(Malvern, U.K.) was used to determine isoelectic point of
alumina by a potentiometric titration. This instrument can
measure particle sizes from 0.6 nm to 6 m. Series of
 616
samples containing (0.05–1)g Al2 O3 /25 ml KNO3 solutions
Downloaded By: [Milonjić, Slobodan K.] At: 08:27 9 July 2008
of different initial pH values were shaken mechanically
in PVC vessels for 24 h at room temperature. Then, the
samples were placed in a sample container and  potentials
were calculated by the instrument software (Smoluchowski
equation). Potentiometric titrations were performed in the
acid region, from pH ≈ 4 to pH ≈ 9, and in the alkaline one,
from pH ≈ 9 to pH ≈ 4 with 0.1 M KOH and 0.1 M HNO3 ,
respectively. Aggregated particle diameters were measured
simultaneously with electrokinetic potential of the alumina
single particle.
Results and discussion
The method for determination of the point of zero charge,
pHpzc , of -alumina as a function of pH and ionic strength
of electrolytes is presented in Fig. 1.
The plateaus obtained at pH 54 ± 01 correspond to the
point of zero charge of as-received commercial -alumina
at 0.100 g/25 ml alumina/solution ratio. For as much as the
value of pHpzc is the same for all electrolyte concentrations
(0.001, 0.01, and 0.1 mol dm−3 ), it means that pHpzc
is independent of the ionic strength of KNO3 , i.e., KNO3 is
an indifferent (inert) electrolyte.
Previously [10], we have determined pHpzc values for
three samples of commercial aluminium oxide (Merck,
Alcan RA45E, and Alcoa CT 3000SE) and obtained the
values 6.8, 6.3, and 6.9, respectively. According to crystal
structure analyses, made by x-ray diffraction, the Merck
powder was a low-temperature -alumina, while Alcan
RA45E and Alcoa CT3000SE powders were -alumina.
When compared to these data, the pHpzc value of the
AKP-30 alumina powder is relatively low. However, this
value is in good agreement with the pHpzc value (5 to 6)
obtained by Stack et al. [11] for a single crystal face of
corundum (sapphire; -Al2 O3 .
Figure 1.—pHf vs. pHi of alumina suspensions. Different concentrations of
KNO3 , as a background electrolyte, are given in mol dm−3 .
J. J. GULICOVSKI ET AL.
Figure 2.—Determination of pHpzc of alumina in 0.01 M KNO3 at different
solid/liquid ratios.
Figure 2 presents the dependence of pHf on pHi for
different alumina/solution ratios. The plateaus obtained
correspond to pHpzc values.
As it can be seen, there is no difference in pHpzc
values for alumina/solution ratios up to 0.5 g/25 ml. Further
increase of this ratio (up to 2 g/25 ml) leads to a slight
increase of pHpzc (from ∼54 to ∼6).
In our previous work [10], we have investigated
the influence of the solid/liquid ratio on the pHpzc of three
commercial alumina powders (Merck, Alcan RA45E, and
Alcoa CT3000Se). It was shown that the increase in
alumina/solution ratios up to 2.0 g/25 ml leads to an increase
in pHpzc value from ≈68 to ≈84 for Merck and Alcoa
CT3000SE powders. This increase in pHpzc we have
explained by the transformation of alumina powder surfaces,
occurring during their hydration in water or electrolyte in
which pHpzc was determined, to surface layer of bayerite–
gibbsite alumina.
A slight increase in pHpzc with increasing
alumina/solution ratio for AKP-30 alumina powder in
comparison with other alumina samples [10] can be
explained by lower solubility of AKP-30 alumina. It is
known that dissolution of various alumina powders
is more pronounced at lower (<5) than at higher (>9)
pHs [10, 12–18]. Usually, pH of the minimum solubility
coincides with the pHpzc of investigated alumina samples
[10, 12, 16, 17]. For example, solubility of -Al2 O3 is for
two orders of magnitude lower than that of -Al2 O3 [16].
It is well known that pHpzc = pHiep in the absence of
specific interaction of the dispersed phase with electrolyte
ions. Considering that, measurements of pHiep of alumina
AKP-30 were performed. The zeta potential of alumina
(-Al2 O3 ) at different concentrations of aqueous KNO3
solutions at 25 C was determined as a function of pH, and
the results are presented in Fig. 3. Before measurements, the
alumina suspensions were equilibrated at pH = 35 for 24 h.
 POINT OF ZERO CHARGE
Downloaded By: [Milonjić, Slobodan K.] At: 08:27 9 July 2008
Figure 3.—The zeta potential of -Al2 O3 as a function of pH at 25 C for
different concentrations of KNO3 .
The titration started at pH ≈ 4, which is far from the
solubility minimum of alumina [10, 12–18]. The value of
zeta potential decreases with increasing suspension pH and
increasing KNO3 electrolyte ionic strength. The position of
the common intersection point accords with  = 0 at pH
86 ± 01 and represents the isoelectric point of -alumina
powder. Since the pHiep is not affected by the electrolyte
concentration, KNO3 is, as in the case of pHpzc , indifferent
electrolyte for the -alumina surface. This result is in
good agreement with electrokinetic data on various alumina
samples obtained by various authors [13, 19–26].
Simultaneously with zeta potential measurements,
particle sizes and aggregation of alumina were measured.
The measured diameters of alumina particles or aggregates
vs. suspension pH are presented in Fig. 4.
Since the titrations started in the acidic region, particles
were positively charged and, due to that charge, suspensions
were stable. Increase in suspension pH leads to zeta potential
decrease and alumina particle-diameter increase. At pH
equal pHiep (8.6), the zeta potential is zero and the suspension
stability decreases due to aggregation of alumina particles.
The aggregation is a function of ionic strength of KNO3 ,
i.e., with increasing concentration of KNO3 solution the
particle diameters increase, even at low pH values, due to
lowering of the thickness of the diffuse part of the electrical
double layer. Dissipation of data in the high pH region is
caused by limitations of the instrument, whose upper limit
of particle diameter measurement is 6 m.
The influence of the alumina/solution ratio on the pHiep
value was also investigated. For 250, 500, and 1000 ppm
suspensions, there is no influence of different solid/liquid
ratios on alumina isoelectric point and pHiep = 84 ± 01.
However, a decrease in solid/liquid ratio leads to the
decrease in pHiep . For solid/liquid ratios of 50 and
100 ppm, pHiep = 74 ± 01. According to Zetasizer Nano
instrument’s User Manual, the minimum concentration of
the solid phase required for zeta potential measurements
depends upon the relative refractive index (the difference in
617
Figure 4.—The dependence of alumina particle diameter on suspension pH
in KNO3 solutions.
refractive index properties of the particle and the medium)
and the particle size. According to our experimental
results, for proper zeta potential measurements of -alumina
in KNO3 electrolyte (0.001–0.1 mol l−1 ), the minimum
concentration of alumina is 250 ppm.
The measured pHiep value (8.6) does not correlate with the
obtained pHpzc value (5.4). Since the used KNO3 electrolyte
is indifferent, i.e., nonspecific towards -alumina surface,
this difference can be explained by the Al2 O3 powder
solubility. Depending on the suspension pH, different ionic
Al-species can be formed Al(OH)2+ , Al(OH)+ 2 , Al(OH)3 ,
Al(OH)− 4 , etc.). Knowing that the solubility of alumina is
lower in the basic than in the acidic region and considering
all above presented results, the following experiment was
performed. The -alumina suspension was equilibrated at
pH = 91 for 24 h, and then the titration was carried out
with 0.1 M HNO3 at pH from ≈9 to ≈4 measuring zeta
potential. The obtained results are presented in Fig. 5. The
measured pHiep = 53 is in excellent agreement with the
pHpzc obtained in this study (54 ± 01). In the same figure,
the results of titration, with 0.1 M KOH, for the alumina
suspension equilibrated at pH = 35 for 24 h were also
presented for comparison.
According to the results obtained, we can conclude
that equilibration suspension pH is a very important
parameter in zeta potential measurement in the case of
soluble oxides, such as Al2 O3 . It is reasonable to assume
that the equilibration pH of alumina suspension, and
hence the presence of various Al-species, will be directly
correlated with the measured pHiep . If alumina dispersion
was equilibrated at low pH value and then titrated with
a base, because of high solubility of alumina powder in
the acidic region, the obtained value of pHiep = 86 would
not correspond to the Al2 O3 surface but to some other
Al-species, probably Al(OH)3 .
It is important to note that for all high pHiep values
(8–9.6), presented in literature [19, 26, 27], equilibration of
 618
Downloaded By: [Milonjić, Slobodan K.] At: 08:27 9 July 2008
Figure 5.—Determination of pHiep of alumina solution equilibrated at
different pHi .
alumina dispersion was performed at low pH value (<5).
According to our best knowledge, this is the first result
obtained on alumina dispersion equilibrated in the alkaline
region, where alumina solubility is lower in comparison
with that in the acidic region and titrated with acid.
Conclusions
The pHpcz of -alumina powder, determined by batch
equilibration method to be 54 ± 01, is independent
of the ionic strength of KNO3 solution. There is no
deference in pHpzc values for alumina/solution ratios up
to 0.5 g/25 ml. Due to solubility of Al2 O3 powder and
formation of Al(OH)3 onto alumina surface, further increase
in sold/liquid ratio (up to 2 g/25 ml) slightly increases the
value of pHpzc .
pHiep depends on the acidity of the solution used for
equilibration of alumina suspension. For the suspension
equilibrated in the acidic region, pHiep has a value of 86 ± 1,
which is close to the value of pHiep of Al(OH)3 . However,
when the equilibration was performed in the alkaline region,
pHiep has a value of 5.3, which corresponds to the value of
pHpzc obtained by batch equilibration method.
Acknowledgment
The authors are grateful to the Ministry of Science
of the Republic of Serbia for financial support (Project
No. 142004).
References
1. Parks, G.A. The isoelectric points of solid oxides, solid
hydroxides, and aqueous hydroxo complex systems. Chem. Rev.
1965, 65, 177–197.
2. Kosmulski, M. Chemical Properties of Material Surface; Dekker:
New York, 2001; 65–309.
3. Kosmulski, M. The pH-dependent surface charging and the points
of zero charge. J. Colloid Interface Sci. 2002, 253, 77–87.
J. J. GULICOVSKI ET AL.
4. Kosmulski, M. pH-dependent surface charging and points
of zero charge II. J. Colloid Interface Sci. 2004, 275,
214–224.
5. Kosmulski, M. pH-dependent surface charging and points
of zero charge III. J. Colloid Interface Sci. 2006, 298,
730–741.
6. Milonjić, S.K.; Ruvarac, A.; Šušić, M. The heat of immersion of
natural magnetite in aqueous solutions. Termochim. Acta. 1975,
11, 261–266.
7. Milonjić, S.K.; Ruvarac, A.; Šušić, M. Adsorption of hydrogen
and hydroxide ions at the natural magnetite-aqueous electrolyte
interface. Bull. Soc. Chim. Beograd. 1978, 43, 207.
8. Milonjić, S.K.; Kopečni, M.M.; Ilić, Z.E. The point of zero charge
and adsorption properties of natural magnetite. J. Radioanal.
Chem. 1983, 78, 15.
9. Čerović, Lj.S.; Milonjić, S.K.; Bahloul-Hourlier, Dj.; Doucey, B.
Surface properties of silicon nitride powders. Colloids Surfaces
A 2002, 197, 147–156.
10. Todorović, Ž.; Milonjić, S.K.; Dondur, V.T. The influence of the
solid/liquid ratio on the point of zero charge of alumina. Mater.
Sci. Forum 2004, 453–454, 361–366.
11. Stack, A.G.; Higgins, S.R.; Eggleston, C.M. Point of zero
charge of a corundum-water interface probed with optical second
harmonic generation (SHG) and atomic force microscopy (AFM):
New approaches to oxide surface charge. Geochim. Cosmochim.
Acta. 2001, 65, 3055–3063.
12. Tombácz, E.; Szekeres, M. Interfacial acid-base reactions of
alumina oxide dispersed in aqueous electrolyte solutions. 1.
Potentiometric study on the effect of impurity and dissolution of
solid phase. Langmuir 2001, 17, 1411–1419.
13. Harju, M.; Halme, J.; Järn, M.; Rosenholm, J.B.; Mäntylä, T.
Influence of aqueous aging on surface properties of plasma
sprayed oxide coatings. J. Colloid Interface Sci. 2007, 313,
194–201.
14. Weerasooriya, R.; Aluthpatabendi, D.; Tobschall, H.J. Charge
distribution multi-site complexation (CD-MUSIC) modeling of
Pb(II) adsorption on gibbsite. Colloids Surfaces A 2001, 189,
131–144.
15. Desset, S.; Spalla, O.; Cabane, B. Redispersion of alumina
particles in water. Langmuir 2000, 16, 10495–10508.
16. Goyne, K.W.; Zimmerman, A.R.; Newalkar, B.L.; Komarneni,
S.; Brantley, S.L.; Chorover, J. Surface charge of variable
porosity Al2 O3 (s) and SiO2 (s) adsorbents. J. Porous Mat. 2002,
9, 243–256.
17. Lefèvre, G.; Duc, M.; Fedoroff, M. Effect of solubility on
the determination of the protonable surface site density of
oxyhydroxides. J. Colloid Interface Sci. 2004, 269, 274–282.
18. Parks, G.A. Free energies of formation and aqueous solubilities
of aluminium hydroxides and oxide hydroxides at 25 C. Am.
Mineral. 1972, 57, 1163–1189.
19. Kosmulski, M.; Dahlsten, P.; Prochniak, P.; Rosenholm, J.B.
Electrokinetics at high ionic strengths: alumina. Colloids Surf.
A. 2007, 301, 425–431.
20. Laucournet, R.; Pagnoux, C.; Chartier, T.; Baumard, J. Catechol
derivatives and anion adsorption onto alumina surfaces in
aqueous media: influence on the electrokinetic properties. J. Eur.
Ceram. Soc. 2001, 21, 869–878.
21. Hackley, V.A.; Patton, J.; Lum, L.S.H.; Wasche, R.J.; Naito,
M.; Abe, H.; Hotta, Y.; Pendse, H. Analysis of the isoelectric
point in moderately concentrated alumina suspensions using
 POINT OF ZERO CHARGE
electroacoustic and streaming potential methods. J. Disp. Sci.
Downloaded By: [Milonjić, Slobodan K.] At: 08:27 9 July 2008
Technol. 2002, 23, 601–617.
22. Johnson, S.B.; Brown, G.E., Jr.; Healy, T.W.; Scales, P.J.
Adsorption of organic matter at mineral/water interfaces. 6.
Effect of inner-sphere versus outer-sphere adsorption on colloidal
stability. Langmuir 2005, 21, 6356–6365.
23. Kershner, R.J.; Bullard, J.W.; Cima, M.J. Zeta potential
orientation dependence of sapphire substrates. Langmuir 2004,
20, 4101–4108.
24. López Valdivieso, A.; Reyes Bahena, J.L.; Song, S.; Herrera
Urbina, R. Temperature effect on the zeta potential and fluoride
View publication stats
619
adsorption at the -Al2 O3 /aqueous solution interface. J. Colloid
Interface Sci. 2006, 298, 1–5.
25. Rowlands, W.N.; O’Brien, R.W.; Hunter, R.J.; Patrick, V. Surface
properties of alumina hydroxide at high salt concentration.
J. Colloid Interface Sci. 1997, 188, 325–335.
26. Beattie, J.K.; Cleaver, J.K.; Waite, T.D. Anomalous aggregation
behaviour of alumina oxyhydroxides. Colloids Surfaces A 1996,
111, 131–138.
27. Johnson, S.B.; Scales, P.J.; Healy, T.W. The binding of
monovalent electrolyte ions on -alumina. I. Electroacoustic
studies at high electrolyte. Langmuir 1999, 15, 2836–2843.