Electrokinetic properties of hybrid pigments

obtained via adsorption of organic dyes

on the silica support
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk
Institute of Chemical Technology and Engineering, Poznan University of Technology, Poznan, Poland

Abstract
Purpose – The purpose of this paper is to characterise the electrokinetic properties of pigments supported on both unmodified and modified silica.
The paper describes the preparation of hybrid pigments via adsorption of organic dyes on silica supports and determination of the zeta potential and
electrophoretic mobility of the materials obtained.
Design/methodology/approach – The materials studied were hybrid pigments obtained as a result of adsorption of two basic dyes: C.I. Basic Red 1
and C.I. Basic Orange 14 and one acidic dye C.I. Mordant Red 3 from solutions of concentrations of 500, 2,000 and 3,000 mg/dm3 on the surface of both
unmodified and modified silica supports. The agent used for modification of the silica surface was N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.
Findings – The modification of the silica surface with aminosilane was found to change, significantly, the electrokinetic character of the inorganic
support. This change was interpreted as being due to the ionisation of ZNH2 groups from the modifier molecule, which changes the surface charge.
Electrokinetic curves of the pigment composites changed considerably as a function of the type and concentration of the organic dye adsorbed.
Research limitations/implications – Only SiO2 supports (unmodified and aminosilane-grafted) and C.I. Basic Red 1, C.I. Basic Orange 14 or C.I.
Mordant Red 3 dyes adsorbed on its surface were evaluated. Other dyes could also be studied.
Practical implications – Measurements of the zeta potential were used to characterise the stability of colloidal dispersions of paints or dyes and to
control the stability of paints on storage and their performance on painting and drying.
Originality/value – The paper demonstrates that the measurements of zeta potential permit determination of the optimum conditions for the use of a
given pigment. The finding of the change of the zeta potential of a given pigment and so, also its application properties as a result of different
functional groups in the dye or the modifying agent molecules.

Keywords Dyes, Pigments, Silicates, Zeta potential, Electrophoretic mobility, Hybrid pigments, SiO2 support, Organic dyes

Paper type Research paper

Introduction van der Waals-London forces whereas the repulsing electric

Electrokinetic (zeta) potential is a very important parameter
that describes the surface properties of solid particles
suspended in water solution (Jesionowski, 2003). It is the
potential difference at the shear plane between the diffuse and
the stationary layer of electric double layer. It appears on the
movement of charged particles in the diffuse layer or on the
movement of the diffuse layer with the help of a stationary
wall. The distance from the shear plane to the particle surface
depends on the zeta potential. The origin and role of zeta
potential is described in details elsewhere (Szymczyk et al.,
1998; Kosmulski, 1999, 2001, 2009; Greenwood, 2003;
Zembala, 2004; Lam et al., 2007; Hunter, 2010). The
implication of zeta potential should not be understood outside
the chemistry of colloids (Kosmulski, 2001). According to the
general theory of stability of lyophobic colloids, developed by
Derjaguin, Londan, Verwey and Overbeek, known as the
DLVO theory, two particles suspended in water are subject to
The current issue and full text archive of this journal is available at
www.emeraldinsight.com/0369-9420.htm
Pigment & Resin Technology
41/1 (2012) 9–19
q Emerald Group Publishing Limited [ISSN 0369-9420]
[DOI 10.1108/03699421211192235]
force, as a consequence of overlapping of the electric layers
coating the two particles. The theory is described in details
elsewhere (Yoon and Mao, 1996; Wu et al., 1999; Missana
and Adell, 2000).
Knowledge of zeta potential permits calculation of the energy
of interaction between two colloidal particles. On the basis of
this energy it is possible to estimate the stability (limitation of
coagulation), viscosity and floating properties of a dispersion
and adjust reagents modifying these properties to get a product
meeting the target properties (Kosmulski, 2001). High positive
or negative value of zeta potential (^30 mV) means that the
system is electrokinetically stable, if the potential is zero the
system is in the state of full coagulation. The pH value at which
the zeta potential is zero is known as the isoelectric point
(i.e.p.). At this point the negative and positive charges take the
same value and the colloidal system is the least stable
(Wongsagousup et al., 2005).
The zeta potential is the first experimentally determinable
value introduced to characterise the electric double layer. It has
been established that the value of zeta potential depends, for
example, on the type of solid-state suspended, character of the
surface of suspended particles, pH of suspension (pH change
influences the surface charge), ionic strength of the dispersion
This work was supported by the Poznan University of Technology
research grant No. 32-125/2010-DS.

9
 Hybrid pigments obtained via adsorption of organic dyes
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk
medium and type of electrolyte used. The influence of the ionic
strength and type of electrolyte on the zeta potential value has
been of interest to many authors (Suhara et al., 1995; Alkan et al.,
2005a, b, c; Kosmulski et al., 2007; Singh and Song, 2007).
Even a small amount of a compound adsorbed on the surface of
suspended particles significantly changes the surface charge and
also the zeta potential value. Thus, modification of the silica
surface with silanes has great effect on the zeta potential.
Analysis of this effect for selected silanes has been reported in
other papers (Kosmulski and Eriksson, 2000; Tsai and Wu,
2004; Alkan et al., 2005a, b, c; Demirbaş et al., 2007;
Jesionowski et al., 2010).
As zeta potential informs about the chemistry of the colloid
particle surface and the colloid system stability, its knowledge
permits selective use of a given substance, so measurements of
zeta potential have been of increasing interest in industries.
For instance, they are important for the process of producing
stable colloidal dispersions for paints or dyes. Zeta potential
characterises the stability and performance of pigments upon
deposition and drying, so its measurements permit
establishment of the optimum conditions of their
exploitation. Alkyl, epoxy, acryl or other functional groups
present in the structure of the dye or the modifying agent,
significantly affect the zeta potential of pigments (Jesionowski,
2005). Values of the zeta potential of pigments on different
supports are given elsewhere (Fujitani, 1996; Jesionowski,
2002; Xu et al., 2003; Croll and Taylor, 2007).
This study was undertaken to characterise the electrokinetic
properties of pigments supported on both unmodified and
modified silica. Functionalisation of the silica surface was made
using alkoxysilane with amine functional groups. Pigments
were obtained with selected organic dyes containing acidic and
basic groups. The criterion of the choice of dyes was the
content of different functional groups capable of interacting
with inorganic supports, in particular with functionalised
aminosilane. The presence of these groups and the acidic or
alkaline character of the dyes determine the distribution density
of positive or negative surface charge. The influence of
modification of the silica surface, the type and concentration of
the organic dye on the zeta potential of the pigments obtained
was determined.
Experimental
Preparation and functionalisation of silica surface
The monodisperse silica studied was precipitated from a
solution of sodium silicate including 27.18 percent SiO2,
8.50 percent Na2O and silicate modulus 3.3 (VITROSILICON
SA). The precipitating agent was a 5 percent solution of HCl
and the organic phase was cyclohexane (POCh SA). The
emulsifying agents contained a mixture of non-ionic surfactants
NP3 and NP6 (PCC ROKITA SA). Two emulsions were
prepared: the first labelled E1 was composed of 20 percent
solution of sodium silicate, cyclohexane, mixture of NP3 and
NP6, while the second labelled E2 contained cyclohexane,
5 percent solution of HCl and a mixture of NP3 and NP6. The
appropriate portion of the emulsifier (NP3 and NP6) was
dissolved in cyclohexane and then the whole system was added
to a 5 percent HCl solution. The solution obtained in this way
was homogenised for 30 min at 19,000 rpm. E1 emulsion was
prepared in a similar way; the difference was that instead of HCl
solution, a 20 percent solution of sodium silicate was used.
E1 emulsion was homogenised in the same conditions.
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Pigment & Resin Technology
Volume 41 · Number 1 · 2012 · 9 –19
To introduce the functional groups on silica surface,
a silane proadhesive compound n-2-(aminoethyl)-3-
aminopropyltrimethoxysilane was used, known under the
commercial name of U-15D and of the chemical formula
H2N(CH2)2NH(CH2)3Si(OCH3)3 made by UniSil. The
aminosilane was preliminary hydrolysed in methanol/water
system (4/1 v/v) at pH 3. The modifying agent was deposited
using the method of atomisation, in the amount of three weight
parts by mass of SiO2.
Preparation of SiO2/organic dye and SiO2/alkoxysilane/
organic dye hybrid pigments
To obtain the pigments, a solution of a given organic dye in one
of the concentrations of 500, 2,000 or 3,000 mg/dm3 was
introduced into a flask containing the silica support. The
hybrids were stirred with a magnetic stirrer IKAMAG R05
made by Ika Werke (Germany) for 2 h. The coloured silica was
filtered off under reduced pressure and dried in a stationary
drier at 1058C for 48 h. The organic dyes used for adsorption on
the silica support were purchased from Sigma-Aldrich (Table I).
Method of electrokinetic (zeta) potential measurement
Measurements of the zeta potential and electrophoretic mobility
of the pigment composites of the type SiO2/organic dyes and
SiO2/aminosilane/organic dyes were made with the use of a
Zetasizer Nano ZS instrument made by Malvern Instruments
Ltd, equipped with an autotitrator. The instrument operates on
the basis of a combination of electrophoresis and laser
measurement of particle mobility employing the Doppler
phenomenon. The instrument measures the velocity of particles
moving in a medium to which an external electric field is
applied. The velocity of a particle in an electric field is known as
its electrophoretic mobility. The experimentally measured
electrophoretic mobility is used to calculate the zeta potential
from the Henry equation (1):
21zf ðKaÞ
UE ¼ ð1Þ
3h
where: UE, electrophoretic mobility; 1, dielectric constant;
j, electrokinetic (zeta) potential; h, viscosity; f(Ka), the Henry
function.
To measure the zeta potential and electrophoretic mobility,
a sample of a given pigment hybrid was suspended in a solution of
an electrolyte (0.001 M NaCl) and placed in a measuring cell.
The pigment suspension was continuously stirred. The system
was titrated with the solutions of 0.2 M HCl and 0.2 M NaOH,
whereas pH values were measured by a glass electrode. The use
of autotitrator permitted accurate dosing of appropriate amounts
of the acid or base to achieve a desired pH. Measurements were
performed in the pH range from 2 to 11. A sample of the known
pH was pumped into a capillary cell inside the Zetasizer Nano ZS
(Malvern Instruments Ltd) instrument in which the
electrophoretic mobility was measured. On the basis of these
measurements the zeta potential was calculated.
Results and discussion
The zeta potential dependence on pH of the pigments
obtained by adsorption of C.I. Basic Red 1 on unmodified
silica support is shown in Figure 1(a).
Electrokinetic properties of silica significantly depend on
the type of substance adsorbed on its surface. The
electrokinetic curves obtained for the hybrid pigments were
 Hybrid pigments obtained via adsorption of organic dyes Pigment & Resin Technology
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk Volume 41 · Number 1 · 2012 · 9 –19

Table I The organic dyes used for pigments preparation

Name Molecular formula Structural formula
C.I. Basic Red 1 C28H31N2O3Cl + –
N O N Cl
H H

CO2CH2CH3

C.I. Basic Orange 14 C17H19N3

N N N

C.I. Mordant Red 3 C14H7O7SNa O OH

OH

SO3Na
O

Figure 1 Zeta potential (A) and electrophoretic mobility (B) versus pH of unmodified silica and hybrid pigments, obtained as a result of adsorption of
C.I. Basic Red 1 on this support

(a) (b)

compared with the curve obtained for unmodified silica in
order to establish changes in the zeta potential and i.e.p.
values (bringing indirect information on acidity or basicity of
the surface) caused by adsorption of C.I. Basic Red 1 from
solutions of three different concentrations. According to many
authors, the i.e.p. of unmodified silica usually falls in the
pH range from 1.7 to 2. Small differences in i.e.p. appear
because of the method of production, conditions of storage
and surface properties of SiO2. The surface charge of silica is
a result of dissociation of silanol groups (Xu et al., 2003).
According to presented measurements, the zeta potential of
unmodified silica took negative values in the whole pH range
analysed. High stability of the system was achieved for
the potential 2 40 to 260 mV for pH varied from 3 to 10.
For this silica the i.e.p. was not reached, but the shape of the
electrokinetic curve suggests that i.e.p. would be reached at pH
near 1.7. Low value of i.e.p. is probably a consequence of high
content of carbon in the unmodified silica structure
which follows from the proposed method of silica support
synthesis. The courses of electrokinetic curves of the pigment

11
 Hybrid pigments obtained via adsorption of organic dyes
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk
composites SiO2/C.I. Basic Red 1 have similar character to that
of unmodified silica. The zeta potential of the pigments took
negative values in the whole pH range analysed and no i.e.p. was
reached. With increasing concentration of dye, the
electrokinetic curves are shifted towards higher pH values.
The zeta potential of the pigment composite obtained after
adsorption of C.I. Basic Red 1 from a solution of 500 mg/dm3
varies from 2 8 to 262 mV, whereas, after the adsorption of dye
from a solution of 3,000 mg/dm3 it varies from 2 8 to 2 50 mV.
The zeta potential is directly proportional to the
electrophoretic mobility, which is shown in Figure 1(b),
showing the electrophoretic mobility versus pH for the same
hybrid pigments. The shape of these curves is almost the same as
that of the zeta potential. The electrokinetic curve obtained for
unmodified silica indicates that the electrophoretic mobility
values are negative over the whole pH range considered. The
character of the curves is analogous to that of the zeta potential,
for example, with increasing concentration of dye adsorbed, the
curves were shifted towards higher pH.
Zeta potential versus pH of the silica modified with 3 wt/wt of
n-2-(aminoethyl)-3-aminopropyltrimethoxysilane (U-15D)
and analogous curves for the pigment composites obtained as
a result of C.I. Basic Red 1 adsorption on modified silica are
shown in Figure 2(a).
Modification of silica surface with n-2-(aminoethyl)-3-
aminopropyltrimetoxysilane in the amount of 3 wt/wt causes a
distinct shift of the electrokinetic curve towards higher pH value,
relative to the curve obtained for unmodified silica. The reason
is the ionisation of ZNH2 groups present in the molecule of the
modifying agent. Ionisation of these groups plays a very
important role in changing the surface charge of the pigment.
High density of Hþ ions induces NHþ 3 appearance so that
positive charge appears on the surface of the modified silica
(ionisation effect). With increasing concentration of Hþ ions
the process of ionisation gets restricted and the surface charge
decreases (Pham et al., 2007). The above behaviour is described
by equations (2) and (3):
Figure 2 Zeta potential (A) and electrophoretic mobility (B) versus pH of silica modified with 3 wt/wt of U-15D silane and hybrid pigments, obtained by
adsorption of C.I. Basic Red 1 on this support
(a)
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Pigment & Resin Technology
Volume 41 · Number 1 · 2012 · 9 –19
ZNH2 þ Hþ ! ZNHþ
3 ð2Þ
ZNH2 þ OH2 ! ZNH2 þ H2 O ð3Þ
The bonding of aminosilane to silica surface is shown in
Figure 3.
Modification with amine compounds leads to high
i.e.p. values of the functionalised silica, which is related to
the alkaline properties of the surface. The zeta potential of
modified silica took positive values in the whole acidic
pH range. The i.e.p. was reached at pH close to 8.1. High
stability of the system was reached for pH from 1.7 to 6, over
which the zeta potential varied from 60 to 30 mV and for pH
from 8 to 10 at which the zeta potential took values from 230
to 2 58 mV. Adsorption of the basic dye C.I. Basic Red 1 on
modified silica caused additional shift of the electrokinetic
curves towards higher pH values and a shift of i.e.p. towards
more acidic pH values. For the silica modified with C.I. Basic
Red 1 adsorbed from the solution of the concentration of
500 mg/dm3, the i.e.p. value was 8.7, while for the silica
modified with the same dye adsorbed from the solution of the
concentration 3,000 mg/dm3, the electrokinetic curve
significantly is shifted and i.e.p. was achieved at pH of 6.8.
These results confirm the chemical character of the dye
adsorption on the surface of the modified SiO2 (Figure 4).
Figure 5 shows the FT-IR spectra of silica unmodified and
modified with 3 wt/wt of U-15D silane. In the process of silica
synthesis the organic phase was cyclohexane and the
emulsifier was a mixture of NP3 and NP6 responsible for
the presence of CZH groups on the silica surface.
The FT-IR spectra show a broad band covering the range
3,600-3,200 cm2 1 assigned to the water physically bound
with silica surface. The band, assigned to the even silanol
groups (vicinal), appears at 3,660 cm2 1 and its intensity
decreases after silica modification. At 2,965-2,850 cm2 1 there
is a band assigned to the CZH bonds. The presence of this
band in the spectrum of unmodified silica is a consequence
(b)
 Hybrid pigments obtained via adsorption of organic dyes Pigment & Resin Technology
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk Volume 41 · Number 1 · 2012 · 9 –19

Figure 3 Scheme of silica surface modification with n-2-(aminoethyl)-3-aminopropyltrimethoxysilane

NH2

NH

NH2

SiO2 NH
+ H2N(CH2)2—NH(CH2)3Si(OH)3 SiO2
NH

Unmodified N-2-(aminoethyl) NH2

silica surface -3-aminopropyltrimethoxysilane
NH

NH2

NH2 NH3+

+H N
3
NH
SiO2 NH3+
NH2 +
H3N
+
NH3+
NH +H NH3+
SiO2
NH
+OH–
NH2
–H2O NH–
–HN NH–
NH
NH–
–HN SiO2
NH2 NH–
–HN
NH–

of its precipitation in the emulsion environment. After the
modification with a U-15D silane, the intensity of the band
assigned to silanol groups (at 3,660 cm2 1) decreases, while
that of the CZH band slightly increases, which is the evidence
of chemical character of the silica surface modification with
n-2-(aminoethyl)-3-aminopropyltrimethoxysilane. As a result
of this modification, the intensity of the band assigned to the
silanol groups decreases, which is interpreted as a
consequence of the condensation reaction of these groups
with the hydroxyl groups of silane.
Figure 2(b) shows the electrophoretic mobility versus pH
for modified silica and pigments obtained by the adsorption of
C.I. Basic Red 1 from solutions of three different
concentrations on the functionalised support. The curve
obtained for modified silica shows the electrophoretic
mobility change in the range 3.8 to 2 3.7 mcm/V for pH
from 2 to 10. With increasing concentration of C.I. Basic
Red 1 in the solution from which it was adsorbed the
electrokinetic curves are shifted towards more basic pH.
Figure 6(a) shows the zeta potential as a function of pH for
hybrid pigments obtained as a result of the adsorption of basic
dye C.I. Basic Orange 14 on unmodified silica support. With
increasing concentration of the solution from which the dye
was adsorbed, the electrokinetic curve shifted towards
higher pH, relative to the position corresponding to
unmodified silica. For the pigment obtained after the
adsorption of C.I. Basic Orange 14 from the solution of
3,000 mg/dm3 the i.e.p. was observed at pH ¼ 2.45. High
stability of the system was reached for pH from 5 to 10 for
which the zeta potential varied from 2 30 to 2 57 mV.
For C.I. Basic Orange 14 adsorbed from the solution of the
concentration of 500 mg/dm3 on unmodified silica surface the
i.e.p. was not reached but the character of the curve suggested
that it would be obtained at pH close to 1.4. High stability of
the system was reached for pH from 3 to 10 for which the zeta
potential varies also from 230 to 2 57 mV.
Figure 6(b) shows the electrophoretic mobility versus pH
for unmodified silica and pigments obtained as a result of C.I.
Basic Orange 14 adsorption on this support. With increasing
concentration of the dye in the solution from which it was
adsorbed the curves are shifted towards higher pH values. For
the pigment obtained after adsorption of C.I. Basic Orange
14 from the solution of 3,000 mg/dm3, the negative sign of the
electrophoretic mobility changed into positive.
Zeta potential as a function of pH for the pigments
obtained as a result of the adsorption of C.I. Basic Orange
14 on modified silica is shown in Figure 7(a).

13
 Hybrid pigments obtained via adsorption of organic dyes Pigment & Resin Technology
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk Volume 41 · Number 1 · 2012 · 9 –19

Figure 4 The adsorption of C.I. Basic Red 1 on silica support modified with n-2-(aminoethyl)-3-aminopropyltrimethoxysilane
NH2

NH
NH2
CO2CH2CH3
NH H3C CH3
SiO2 +
NH
HN O N
NH2
CH3 HCl CH3
NH
C.I. Basic Red 1
NH2

Aminosilane-grafted
silica support

NH2 CO2CH2CH3
CO2CH2CH3 H3C CH3
H3C CH3 NH
H H
N H
N O N
N O N H CH3 HCl CH3
NH
H 3C HCl H3C SiO2
N
NH2 H

NH

NH2
Pigment composite

Figure 5 FT-IR spectra of unmodified and aminosilane-grafted silica
The electrokinetic curves obtained for modified silica and the
pigments prepared on this support are very similar to the
corresponding curves obtained for unmodified silica and
the pigments obtained using it as a support. Modification of
the silica surface did not result in a considerable shift of the
curves obtained for the pigments towards more basic
pH values and did not change the zeta potential sign. The
pigments obtained by adsorption of the dye from the solution
of a lower concentration were characterised by negative zeta
potential in the whole pH range analysed. With increasing
concentration of the solution from which the dye was
adsorbed the electrokinetic curve shifted towards higher pH,
which was related to the basic character of the dye. Only the
electrokinetic curve obtained for the pigment prepared by
adsorption of the dye from the solution in concentration of
3,000 mg/dm3 reached the i.e.p. at pH of 2.2 (which is a result
similar to that for the pigment obtained after dye adsorption
from the solution of the same concentration on unmodified
silica). The presence of ZNH2 groups in the structure of C.I.
Basic Orange 14 has no effect on the shift of the electrokinetic
curves and does not make the pigments dispersed in water
environment to reach the i.e.p. The pigments obtained,
except SiO2 þ3 wt/wt of U-15D þ 3,000 mg/dm3 C.I. Basic
Orange 14, did not reach the i.e.p.
Figure 7(b) shows the electrophoretic mobility versus pH
for the modified silica and the pigments obtained due to C.I.
Basic Orange 14 adsorption on this support. For these
pigments the electrophoretic mobility values were negative in
the whole pH range analysed. With increasing concentration
of the dye solution from which it was adsorbed, the curves
shifted towards higher pH values. For the pigment obtained

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 Hybrid pigments obtained via adsorption of organic dyes Pigment & Resin Technology
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk Volume 41 · Number 1 · 2012 · 9 –19

Figure 6 Zeta potential (A) and electrophoretic mobility (B) versus pH of unmodified silica and pigments, obtained after adsorption of C.I. Basic Orange
14 on this support

(a) (b)

Figure 7 Zeta potential (A) and electrophoretic mobility (B) versus pH of modified silica and hybrid pigments obtained after adsorption of C.I. Basic
Orange 14 on this support

(a) (b)

by C.I. Basic Orange 14 adsorption from the solution of
3,000 mg/dm3 the i.e.p. was reached at pH near 2.2.
The zeta potential versus pH for the pigments obtained by the
adsorption of C.I. Mordant Red 3 on unmodified silica is shown
in Figure 8(a). The electrokinetic curves of these pigments have
very similar character as the curve obtained for unmodified
silica, irrespective of the concentration from which the dye was
adsorbed. The zeta potential of these pigments was negative in
the whole pH range analysed. This pigments showed high
stability in the pH range from 3 to 10, in which the zeta potential
varied from 2 30 to 255 mV. No i.e.p. was reached. Increased
amount of hydroxyl groups in the dye molecule (related to dye
concentration) resulted in a decrease in the positive charge on
the adsorbent surface.
Figure 8(b) shows the electrophoretic mobility versus pH
for the modified silica and pigments obtained by the
adsorption of C.I. Mordant Red 3 on this support. The
character of the electrokinetic curves obtained is very similar

15
 Hybrid pigments obtained via adsorption of organic dyes Pigment & Resin Technology
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk Volume 41 · Number 1 · 2012 · 9 –19

Figure 8 Zeta potential (A) and electrophoretic mobility (B) versus pH of unmodified silica and hybrid pigments, obtained by adsorption of C.I. Mordant
Red 3 on this support

(a) (b)

to that of the analogous curves for the dyes adsorbed on the
unmodified silica support. The electrophoretic mobility of all
pigments is negative in the whole pH range analysed.
The zeta potential versus pH for the pigments obtained as a
result of C.I. Mordant Red 3 adsorption on the modified silica
surface is shown in Figure 9(a).
The electrokinetic curves of the pigments were shifted
towards higher pH values with respect to those for the pigments
obtained by dye adsorption on the unmodified silica, which is a
consequence of a strong ionisation effect of the amine groups
from U-15D silane. The pigments obtained using modified
silica have positive zeta potential values in a wide range of pH
(1.7-5). With increasing concentration of the solution from
which the dye was adsorbed the curves shifted towards lower pH
and the i.e.p. values decreased, which was related to the acidic
character of the dye. The i.e.p. of the pigment obtained by the
adsorption of C.I. Mordant Red 3 from the solution of 500 mg/
dm3 on the modified silica surface is 4.88, and the system
reached high stability for pH from 7 to 10 as follows from the
zeta potential values from 230 to 250 mV. For the pigment

Figure 9 Zeta potential (A) and electrophoretic mobility (B) versus pH of modified silica and hybrid pigments, obtained as a result of C.I. Mordant Red 3
adsorption on this support

(a) (b)

16
 Hybrid pigments obtained via adsorption of organic dyes
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk
obtained by C.I. Mordant Red 3 adsorption from the solution of
3,000 mg/dm3, the i.e.p. is 3.95 and the system is the most stable
in the pH range from 6 to 10.
The plots of electrophoretic mobility versus pH of the modified
silica and the hybrid pigments obtained as a result of C.I.
Mordant Red 3 adsorption on the silica support are shown in
Figure 9(b). With increasing concentration of the solution from
which the dye was adsorbed the curves were shifted towards more
acidic pH. For the pigment composite produced by the
adsorption of C.I. Mordant Red 3 from the solution of 500 mg/
dm3 on the aminosilane modified silica, the electrophoretic
mobility changes from 2 to 24 mcm/V, while for that adsorbed
from the solution of 3,000 mg/dm3 the corresponding values are
1.2 to 23.7 mcm/V for pH varied from 2 to 11.
Results of the FT-IR spectrophotometric study confirmed the
efficiency of the process of silica surface functionalisation and
adsorption of dyes on the silica support surface (Figure 10),
manifested as a decrease in intensity of the band assigned to
silanol groups (at 3,660 cm2 1) (Figure 11(a) and (b)).
Particularly pronounced changes were observed after the
adsorption of C.I. Basic Red 1. With increasing concentration
of the initial solution of the dye to be adsorbed, the intensity of
the band assigned to the CZH stretching vibrations increases.
The FT-IR spectra of the pigment obtained after the adsorption
of C.I. Basic Red 1 show also a broad band corresponding to the
physically bound water at 3,600-3,200 cm2 1. The spectrum of
the pigment obtained after the adsorption of the dye
from a solution of 3,000 mg/dm3 reveals a band characteristic
Figure 10 Adsorption of C.I. Mordant Red 3 on silica surface modified with n-2-(aminoethyl)-3-aminopropyltrimethoxysilane
NH2
NH
NH2
NH
NH2 NH SiO2
NH
NH2
Aminosilane-grafted
silica support
NH2
NH
O OH
OH
SiO2
SO3
O NH2+
NH2
NH
NH2
Pigment composite
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Pigment & Resin Technology
Volume 41 · Number 1 · 2012 · 9 –19
of the NZH functional groups at 3,360-3,240 cm2 1, which
could suggest a bifunctional character of the modification.
The spectra obtained are indirect evidence for the correctness
of the mechanisms proposed (Figure 11(a) and (b)) and hence
for the effectiveness of the process of bifunctionalisation. The
results of analyses performed prove the effectiveness of the
proposed method for obtaining pigment hybrids. The durability
of the materials produced (their colloidal stability) confirmed by
electrokinetic and spectrophotometric studies suggests the
possibility of their use in pigment materials that require specific
physico-chemical properties (pH, type of environment,
compatibility with polymer dispersion, etc.).
Conclusions
The modification of the silica surface with aminosilane
significantly changes the electrokinetic properties of the
support: its zeta potential, electrophoretic mobility and i.e.p.
The effect is evidenced by the shift of the electrokinetic curves
towards higher pH with respect to the curve for unmodified
silica and indirectly by an increase in i.e.p. values, which for
the modified silica is 8.1.
The electrokinetic curves estimated for the hybrid pigments
obtained by C.I. Basic Red 1 adsorption on both unmodified and
modified silica, irrespective of the concentration of the solution
from which the dye was adsorbed, show small differences from
the reference curve (for unmodified silica support). The curves
characterising the pigments were slightly shifted towards higher
O OH
OH
SO3– +H
O
C.I. Mordant Red 3
HO O
HO
NH3+–
O3S
O
NH
 Hybrid pigments obtained via adsorption of organic dyes
Teofil Jesionowski, Magdalena Nowacka and Filip Ciesielczyk
Figure 11 FT-IR spectra of the hybrid pigments obtained as a result of adsorption of (A) C.I. Basic Red 1 and (B) C.I. Mordant Red 3 from solutions of
the concentrations of 500 and 3,000 mg/dm3 on the surface of modified silica
pH values with increasing concentration of the solution from
which the dye was adsorbed, which confirmed the chemical
character of the adsorption of the dye on the silica surface.
The electrokinetic curves of the pigments obtained by the
adsorption of C.I. Basic Orange 14 on unmodified and
modified silica imply negative zeta potential values in the
whole pH range considered. With increasing concentration of
the dye in the solution from which it was adsorbed the curves
are significantly shifted towards alkaline pH values, which was
related to the basic character of the dye. The character of the
electrokinetic curves of these pigments adsorbed on both
unmodified and modified silica is almost identical.
For the pigments obtained as a result of the adsorption of
C.I. Mordant Red 3 (an acidic dye) on modified silica, the
electrokinetic curves were shifted towards more acidic
pH values with increasing concentration of the solution
from which the dye was adsorbed.
The above presented and discussed results have confirmed
that the zeta potential is determined by the chemical character
of the support surface. Even small amounts of organic dye
adsorbed on unmodified or modified silica have considerably
changed the surface charge density and thus also the zeta
potential and stability of the dispersion.
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Further reading
Lima, E.R.A., Boström, M., Biscaia, E.C., Tavares, F.W. and
Kunz, W. (2009), “Ion specific forces between charged self-
assembled monolayers explained by modified DLVO
theory”, Colloids and Surfaces A: Physicochemical and
Engineering Aspects, Vol. 346 Nos 1-3, pp. 11-15.
About the authors
Teofil Jesionowski graduated from the Faculty
of Chemical Technology, Poznan University of
Technology (PUT), receiving the degree of
Master and Engineer of Chemistry. He
defended his doctoral thesis in the Institute of
Chemical Technology and Engineering, PUT in
1999. He has been employed in the Institute of
Chemical Technology and Engineering, Faculty of Chemical
Technology, PUT since 1999 as an associated professor and is
Head of the Division of Chemical Technology. His research and
scientific areas are: surface and colloids science, dyes and
pigments, polymer processing, nanocomposites, and inorganic
environmental pollution protection. Teofil Jesionowski is the
corresponding author and can be contacted at: teofil.
jesionowski@put.poznan.pl
Magdalena Nowacka graduated from the
Faculty of Chemical Technology, Poznan
University of Technology, receiving the degree
of Master and Engineer of Chemistry. She has
been a PhD student in the Poznan University
of Technology, Faculty of Chemical
Technology since 2009.
Filip Ciesielczyk graduated from the Faculty
of Chemical Technology, Poznan University of
Technology (PUT) in 2003, receiving the
degree of Master and Engineer of Chemistry.
He defended his doctoral thesis in the Institute
of Chemical Technology and Engineering,
PUT, in 2007. He has been employed in the
Institute of Chemical Technology and Engineering, Faculty of
Chemical Technology, PUT, since 2007. His research and
scientific areas are: surface and colloids science, dyes and
pigments, polymer fillers, nanocomposites, selective
adsorbents, and inorganic oxide hybrids.
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