Introduction

Contributed paper
Pigments represent the principal colouring
Properties of components of many coating materials,
amorphous silica as including paint. Pigments can also contribute
to a paint’s coating ability. Appropriate
modified by adsorbed properties of a paint formulation or a coating
silane coupling agents layer can be attained only when the properties
of the pigments involved have been fully
and organic dyes characterised (Christie, 2001).
Characteristics of pigments include particle
A. Krysztafkiewicz size and particle shape, oil number, light
S. Binkowski refraction coefficient and solubility in
water (Lambourne and Strivens, 1999).
A. Kaczmarek and The pigment properties should be well
T. Jesionowski characterised and should be reproducible for a
given pigment. Moreover, pigments used in
The authors paint formulations should be stable under the
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and
conditions of their use (e.g. environments of
T. Jesionowski are all at the Poznań University of extreme pH, temperature or illumination)
Technology, Institute of Chemical Technology and (Carter and Bristow, 1998; Guthrie and
Engineering, Poznań, Poland. Kunaver, 1997).
In general, pigments can be grouped into
Keywords organic and inorganic categories. In the last
Silica, Adsorption, Dyes, Pigments 10 years, studies have been carried out on the
preparation of new pigments by adsorption or
Abstract
incorporation of organic dyes onto the
surfaces of various inorganic solids (Aiken
Two types of amorphous silica namely, the precipitated
et al., 1988; Giesche and Matijevic, 1991; Hsu
silica and the pyrogenic silica, were studied. The surfaces
et al., 1992; Tentorio et al., 1980; Wu et al.,
of such silica were modified with silane coupling agents
1997). By varying the physical and chemical
such as 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-
parameters, e.g. particle size or specific
aminopropyltrimethoxysilane and 3-ureidopropyl-
surface area of a starting material, pigments of
trimethoxysilane. Pigments were obtained by the
a desired colour, shade and transparency can
adsorption of organic dyes, C.I. Reactive Blue 19 and
be obtained in a controlled manner through
C.I. Acid Green 16, onto the modified silica surface.
coupling with dyes (Matijevic, 1998). Dyes
Structural properties of the modified silica and the
which are acidic in nature can interact with
pigments obtained were evaluated using scanning
surfaces of an alkaline character, such as
electron microscopy, zeta potential analysis and particle
Al2O3. Dyes which have an alkaline character
size measurement techniques. Moreover, colour of the
can interact with surfaces having an acidic
pigments obtained was evaluated using the CIE L *a*b*
nature, such as silica. If necessary, the core of
colour space system. The specific surface area of the
the pigment particle may be modified to
pigment obtained was estimated using the BET method.
promote interactions with the dyes.
Interactions between solid surfaces and dyes
Electronic access may involve the formation of covalent bonds
or physical attraction forces including
The research register for this journal is available at
electrostatic and/or van der Waal’s forces.
http://www.emeraldinsight.com/researchregister
For example, reactive dyes can be coupled to
The current issue and full text archive of this journal is
The authors are indebted to Boruta-Kolor Sp. z o.o.
available at
for supplying the dyes used in this study and
http://www.emeraldinsight.com/0369-9420.htm
Degussa-Hüls A.G. for supplying the pyrogenic
silica. Furthermore, the authors are indebted to
Medson S. C. for their help in colorimetric
Pigment & Resin Technology
Volume 32 · Number 3 · 2003 · pp. 149– 159
measurements. This work was supported by the
q MCB UP Limited · ISSN 0369-9420 Polish Committee for Scientific Research (KBN)
DOI 10.1108/03699420310475610 Grant, No. 3 T09B 008 19.
149
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

the surface of modified silica to produce Figure 1

water-dispersable pigments, which can be
used in ink-jet printing inks (Galgoci et al.,
1999; Winnik et al., 1990). By the use of a
gradual synthesis of a chromophore on the
surface of silica (Giesche and Matijevic,
1991), azo pigments can be obtained. Such
pigments have found applications in xerox
toners. Recently, pigments obtained by
adsorption of a reactive dye on the surface of
the modified silica have been successfully used
in both water-borne and solvent-borne acrylic
paints (Binkowski and Krysztafkiewicz,
2002). These paint products exhibit a series
of excellent coating properties.
In this paper, results of studies carried out
in order to prepare stable pigments by the
adsorption of organic dyes onto a modified
silica surface are presented. Physicochemical
properties of the pigments prepared were
characterised in order to evaluate the effect of
processing conditions on the physical
properties of the final product.

of the modifier used was always adjusted so

Experimental
that a uniform wetting of silica surface took
Materials place in the mixer. Appropriate solutions of
During the current study, commercially the modifier were added dropwise to the
available silica, Syloid 244 (Grace Davison) silica (Aerosil 200 or Syloid 244) contained
and Aerosil 200 (Degussa-Hüls), were used. in a flask. The solutions were prepared
For the modification of the silica surface, immediately before use for the modification
several silane coupling agents were used. in an attempt to prevent aging. The
Such silane coupling agents included modification was performed in a mixer for 1 h
3-aminopropyltriethoxysilane (U-13, at room temperature. Following the mixing,
H2N(CH2)3Si(OC2H5)3), N-2-(aminoethyl)- the silica was dried at 1058C and passed
3-aminopropyltrimethoxysilane (U15, through a sieve of 0.2 mm mesh.
H2N(CH2)2NH(CH2)3Si(OCH3)3), and
3-ureidopropyltrimethoxysilane (U-17,
H2NC(O)NH(CH3)3Si(OCH3)3), supplied
by UniSil. For the preparation of coloured Colouration of the silica
silica, unpurified organic dyes were used. Fifty cubic centimetre aqueous solution of an
Structures of such organic dyes including C.I. organic dye (Binkowski et al., 2000) of various
Reactive Blue 19 and C.I. Acid Green 16 concentrations and 1 cm3 HCl were
(Boruta-Kolor) are shown in Figure 1. introduced to a conical flask, containing, each
time, 2 g of the modified silica, Syloid 244
(or 0.5 g Aerosil 200). The content of the flask
Modification of silica was mixed with a magnetic stirrer for 4 h at
The surface of the silica was modified with room temperature. Subsequently, the content
silane coupling agents, U-13, U-15 and was filtered under vacuum. The sediment was
U-17. Thus, solutions containing 1, 3 and dried at 1058C. The same procedure
5 parts by weight of the silane coupling agent was repeated for the unmodified silica.
in water, methanol or methanol/water The amount of unadsorbed dye in the filtrate
mixture (4:1) per 100 parts by weight of the was estimated by measuring its visible light
unmodified silica were prepared absorbance using a SECOMAM S 750
(Krysztafkiewicz et al., 2000). The amount spectrophotometer.
150
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Characterisation of the pigments Nitrogen adsorption-desorption isotherms

prepared of the pigment samples were obtained from a
In order to determine the morphology of the volumetric adsorption analyser, ASAP 2010,
pigment surface, selected pigment samples supplied by Micromeritics. The samples
were examined using a scanning electron were first degassed for 2 h at 1208C.
microscope (SEM), which allowed the The measurements of adsorption-desorption
analysis of the fracture plane, of the surface were then carried out at 2 1968C over a
structure and of the status of agglomeration of relative pressure range of 0.010-0.995. The
the pigment. Since silica does not conduct average pore size of the pigment sample was
electric currents, irradiation of its surface with determined by the BJH method, using the
an electron beam of the SEM results in an adsorption isotherm branch.
accumulation of an electric charge, which
affects the quality of the SEM images. In order Results and discussion
to avoid the accumulation of the surface
electric charge, the silica sample was treated Particle size and particle morphology of
with tertiary butyl alcohol. In this study, a the silica and the pigments investigated
Philips SEM 515 SEM was used. Particle size distribution of the unmodified,
Laser Doppler electrophoretic light precipitated silica, Syloid 244, is shown in
scattering determinations were performed Figure 2. Here, it can be seen, that the silica
using a ZetaPlus instrument, supplied by structure consists of aggregates and
Brookhaven Instruments Co. The following agglomerates. Primary particles of silica
conditions were employed: reference beam become coupled to each other by hydrogen
mode was set at the wavelength of the laser bonds at first into primary agglomerates
light source of 635 nm, sampling time was set (aggregates) which, at a further stage, bind to
to 256 ms, modular frequency 250 Hz and form spatial structures of the secondary
the scattering angle 158. The final zeta agglomerates. The decisively more intense
potential distributions were obtained by bands, (Figure 3), present within the range of
averaging 10 runs. 429.4-569.3 nm (maximum intensity of 100
Particles size distribution of the solid corresponding to agglomerate size of
samples was also examined using the ZetaPlus 508.6 nm), characterise the primary
instrument. The particles size was measured structures. A much less intensive band,
using the dynamic light scattering (DLS) related to the formation of the secondary
technique. The technique involved weighing agglomerates, fitted the diameter range of
out an appropriate quantity of sample, placing 1326.3-1758.3 nm (maximum intensity of 39
it in a small amount of water (0.1 g in 50 cm3 corresponding to the diameter of 1484.7 nm).
H2O) and homogenising the sample using an Thus, the unmodified silica exhibited certain
ultrasonic bath (50 KHz). The sample thus lack of homogeneity. The mean particle size of
prepared was placed in a cuvette and the size the silica was 765.0 nm.
distribution of silica particles measured. Surface modification of the Syloid 244 silica
The colorimetric data of the pigments using U-13 aminosilane (5 parts by weight) in
prepared was measured using a Spectro
Module 4000 colorimeter, supplied by JETI
Technische Instrumente GmbH. The Figure 2 Multimodal particle size distribution of the
colorimeter was calibrated using a white unmodified Syloid 244
colour standard tile with tristimulus values:
X ¼ 78:7; Y ¼ 83:1 and Z ¼ 86:5 (Standard
No. 0085). Daylight light source (D65) was
used as a standard. A fixed amount of the
pigment sample was poured into the
measurement cup. The instrument gives the
colour of the samples in terms of the L, a, b
values. L represents the lightness. The
symbols a and b represent the colour
coordinates, where +a is the red direction,
2 a is the green direction, +b is the yellow
direction and 2 b is the blue direction.
151
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

methanol solution practically failed to alter 735.5 nm for the modified silica to 877.7 nm
the silica structure (Figure 3). Presence of for the modified silica surface with adsorbed
both the primary and secondary structures dye. A highly uniform character of the
was noted and band intensities in the two green pigment obtained was indicated by
ranges of agglomerate size were very similar the range of the aggregate diameters of
(Figure 3(a)). The slightly more intensive 872.3-885.8 nm (maximum intensity of 100
band characterised aggregates of corresponding to the diameter of 872.2 nm),
390.4-480.9 nm in diameter (maximum as shown in Figure 4(a). The electron
intensity of 100 corresponding to primary micrograph shows an increase in the
structures of 442.5 nm in size). The band of uniformity of the silica following adsorption of
977-1154.3 nm represented agglomerates the dye, as shown in Figure 4(b).
(maximum intensity of 98 corresponding to The pyrogenic silica, Aerosil 200, exhibited
the diameter of 1061.9 nm). The mean a highly uniform character (Figure 5). The
particle diameter resembled that of the particle size distribution manifested two
unmodified silica particles and amounted to bands within the primary structures, which
735.5 nm. As can be noted in Figure 3(b), the practically fused with each other. The less
aggregates and agglomerates were present in intensive band covered the range of
similar amounts. 84.0-136.0 nm (maximum intensity of
Following adsorption of the green dye, C.I.
Acid Green 16, the modified silica exhibited Figure 4 Multimodal particle size distribution (a) and SEM (b) of Syloid 244
a highly uniform character. However, the modified with 5 parts (by weight) of U-13 silane (in methanol) after
mean particle diameter increased from adsorption of C.I. Acid Green 16

Figure 3 Multimodal particle size distribution (a) and SEM

(b) of Syloid 244 modified with 5 parts (by weight) of U-13
silane (in methanol)

152
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Figure 5 Multimodal particle size distribution of the unmodified Aerosil 200 Figure 6 Multimodal particle size distribution (a) and SEM
(b) of Aerosil 200 modified with 3 parts (by weight) of
U-15 silane (in water)

48 corresponding to the aggregate diameter

of 106.9 nm). On the other hand, the more
intensive band spanned the range of
136.0-248.1 nm (maximum intensity of 100
corresponding to the aggregate diameter
of 195.0 nm). The mean diameter of Aerosil
200 aggregates was 186.1 nm.
Modification of the Aerosil 200 surface
with aqueous solution of U-15 aminosilane
resulted in the deterioration of its morphology
and agglomerate structure. As can be seen
from the SEM in Figure 6(b), the particle
sizes were extremely variable, and large
secondary agglomerates were formed. Particle
size distribution of aminosilane-modified
Aerosil 200 indicated the presence of three
bands (Figure 6(a)). The least intensive band
fitted the range of 79.0-171.8 nm (maximum
intensity of 22 corresponding to the primary intensive band occurred within the range of
structure diameter of 107.8 nm). The most 157.7-284.6 nm (maximum intensity of 100
intensive band was present in the range of corresponding to the diameter of 199.7 nm).
200.7-373.6 nm (maximum intensity of 100 The band reflecting the formation of the
corresponding to the primary structure secondary structure covered the range of
diameter of 273.8 nm). On the other hand, 650.1-1042.4 nm (maximum intensity of
the band reflecting formation of secondary 45 corresponding to the agglomerate diameter
agglomerates spanned the range of of 823.2 nm). Mean particle diameter of the
2813.0-6115.2 nm (maximum intensity of relevant pigment was 345.5 nm.
9 corresponding to the secondary structure
diameter of 5235.6 nm). The mean particle
diameter of the modified Aerosil 200 silica Zeta potential and polydispersity of the
was 534.4 nm. silica and the pigments prepared
Adsorption of the organic dye, C.I. As evident from the data in Table I,
Reactive Blue 19, on the surface of Aerosil aminosilane modification of Syloid 244 silica
200 resulted in a pronounced tendency to and dye adsorption resulted in a decrease in
form secondary agglomerates (Figure 7). the zeta potential from 2 39.40 mV for the
After binding the dye, the particle size unmodified silica to 2 15.16 mV for the silica
distribution also indicated three bands with adsorbed dye. The silica-based pigment
(Figure 7(a)). The least intensive band obtained exhibited low polydispersity (of the
covered the range of 54.5-77.7 nm (maximum order of 0.005) which was very significant
intensity of 23 corresponding to the aggregate compared to the polydispersity value of 0.132
diameter of 69 nm). In turn, the most for the unmodified silica. Thus, the pigment
153
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Figure 7 Multimodal particle size distribution (a) and SEM had an almost monodisperse nature. In the
(b) of Aerosil 200 modified with 3 parts (by weight) of case of Aerosil 200, modification resulted in a
U-15 silane (in water) after adsorption of C.I. Reactive decrease in the zeta potential (the dispersion
Blue 19 was less stable) but dye adsorption caused an
increase in the zeta potential (and gave a more
stable dispersion).

Efficiency of the dyes adsorption on the

silica surface
As shown in the data in Table II, the efficiency
of the adsorption of C.I. Reactive Blue 19 dye
on the silica surface was strongly influenced
by the modification of the surface with silanes.
The lowest efficiency of the dye adsorption
was observed on unmodified surfaces or
surfaces modified with 1 part (by weight) of
aminosilanes U-13 and U-17 (efficiency of
around 40-50 per cent). Silica modification
caused a clearly augmented efficiency of
adsorption. Particularly high efficiencies
(up to 99.8 per cent) were observed on silica
modified with 3 or 5 parts, by weight, of U-13
and U-15 silanes. The higher dye adsorption
efficiency is achieved when more aminosilanes
were used for the modification. A similar
relation was noted when Aerosil 200 was used
as a carrier.
Similar to the adsorption of C.I. Reactive
Blue 19 dye, the silica modification resulted in
an augmented efficiency of adsorption of C.I.
Acid Green 16 dye (Table III), as compared to
adsorption on the unmodified silica.
However, no significant difference in
adsorption efficiencies due to the amount and
the type of the modifier applied was noted.
The efficiencies varied around 73.5 per cent
Table I Zeta potential, polydispersity and mean particle diameter for the in the case of the precipitated silica and
unmodified, the modified and the coloured silica around 47.7 per cent in the case of the
Amount of silane Zeta potential Mean diameter pyrogenic silica.
(weight parts) (mV) Polydispersity (nm)
Syloid 244
Colour characteristics of the pigments
0 239.40 0.132 765.0 prepared
The colour of the pigments obtained was
Syloid 244 + U-13 measured using the colorimeter, as described
5 (m) 217.55 0.142 735.5 earlier and the results are shown in
U-13 + C.I. Acid Green 16 Figures 8-11. The L* value (lightness) of the
5 (m) 215.16 0.005 877.4 pigments obtained by adsorption of C.I.
Reactive Blue 19 on the unmodified Syloid
Aerosil 200
244 silica was the most pronounced. An
0 224.02 0.142 186.1
increase in the amount of U-13 silane, used
Aerosil 200 + U-15 for silica modification in methanol/water,
3 (w) 215.76 0.193 534.4 resulted in a decrease in the lightness of the
pigments obtained, indicating increasing
Aerosil 200 + U-15 + C.I. Reactive Blue 19
amounts of the dye adsorbed on the surface.
3 (w) 221.73 0.262 345.5
This was because the lightness (L*) was
Notes: (w) - modification in water; (m) - modification in methanol measured as the total amount of light reflected
154
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Table II Adsorption extent of C.I. Reactive Blue 19 dye (adsorption time - 4 h)

Dyes concentration Dyes concentration
Amount of silane before adsorption after adsorption Disposal extent
(weight parts) Modification medium (mg/cm3) (mg/cm3) (per cent)
Syloid 244
0 – 0.4 0.4 0.0
Syloid 244 + U-13
5 Water 1.0 0.02715 97.3
5 Water 1.2 0.00330 99.7
5 Methanol 1.0 0.06450 93.6
5 Methanol 1.2 0.12797 89.3
5 Methanol 1.4 0.18173 87.0
5 Methanol 2.0 0.39570 80.2
5 Methanol 2.0 1.13730a 43.1
1 Methanol/water 0.4 0.19596 51.0
1 Methanol/water 1.0 0.06305 93.7
3 Methanol/water 0.2 0.00403 97.9
3 Methanol/water 0.4 0.00820 97.9
3 Methanol/water 0.6 0.02334 96.1
3 Methanol/water 1.0 0.11690 88.3
3 Methanol/water 1.4 0.30050 78.5
5 Methanol/water 1.0 0.01536 98.5
5 Methanol/water 1.2 0.07030 94.1
5 Methanol/water 1.4 0.05679 95.9
Syloid 244 + U-15
5 Methanol 2.0 0.91250 54.4
1 Methanol/water 1.2 0.27240 77.3
3 Methanol/water 1.2 0.30960 74.2
5 Methanol/water 1.2 0.00258 97.9
U-17
1 Methanol/water 1.2 0.72660 39.5
3 Methanol/water 1.2 0.21500 82.1
5 Methanol/water 1.2 0.17565 85.4
Aerosil 200
0 – 2.0 1.5000 25.0
Aerosil 200 + U-15
1 Water 2.0 1.4501 27.5
3 Water 2.0 1.4030 29.9
5 Water 2.0 0.1103 94.5
1 Methanol 2.0 1.4846 25.8
3 Methanol 2.0 1.1772 41.1
5 Methanol 2.0 0.8590 57.1
1 Methanol/water 2.0 1.4501 27.5
3 Methanol/water 2.0 0.3050 84.8
5 Methanol/water 2.0 1.0004 49.9
Note: a 2 0.5 g of modified silica

by the surface. Instead of reflecting, the silica 98.17 and the pigment obtained on silica
surface-adsorbed dyes absorbed a fraction of modified with 5 parts (by weight) of U-15
the incident light, causing a decrease in the aminosilane showed an L* value of 50.48
values of lightness. Obviously, the value of (Figure 8). A similar trend was observed for
lightness depended on the type of the dye pigments obtained by adsorption of the same
applied. In the case of the helactin blue, the dye on Aerosil 200 silica, modified with
pigment obtained by adsorption onto various amounts of U-15 silane in water
unmodified silica exhibited an L* value of (Figure 9).
155
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Table III Adsorption extent of C.I. Acid Green 16 dye (adsorption time - 4 h)
Dyes concentration Dyes concentration
Amount of silane before adsorption after adsorption Disposal extent
(weight parts) Modification medium (mg/cm3) (mg/cm3) (per cent)
Syloid 244
0 – 0.4 0.4000 0.0
Syloid 244 + U-13
1 Water 0.4 0.10474 73.8
3 Water 0.4 0.10486 73.8
5 Water 0.4 0.10517 73.7
1 Methanol 0.4 0.10627 73.4
3 Methanol 0.4 0.10525 73.7
5 Methanol 0.4 0.105531 73.6
5 Methanol 0.4 0.104822 73.8
5 Methanol 0.4 0.105573 73.6
5 Methanol 0.4 0.105094 73.7
5 Methanol 0.4 0.105175 73.7
5 Methanol 2.0 0.106945 94.7
1 Methanol/water 0.4 0.10498 73.8
3 Methanol/water 0.4 0.10474 73.8
5 Methanol/water 0.4 0.10474 73.8
Syloid 244 + U-15
1 Methanol 0.4 0.10513 73.7
3 Methanol 0.4 0.10525 73.7
5 Methanol 0.4 0.10466 73.8
5 Methanol 2.0 1.05570a 47.2
1 Methanol/water 1.2 0.10525 91.2
U-17
1 Methanol 0.4 0.10639 73.4
3 Methanol 0.4 0.10517 73.7
5 Methanol 0.4 0.10462 73.9
Aerosil 200
0 – 2.0 1.5000 25.0
Aerosil 200 + U-15
1 Water 2.0 1.0466 47.7
3 Water 2.0 1.0466 47.7
5 Water 2.0 1.0458 47.7
1 Methanol 2.0 1.0458 47.7
3 Methanol 2.0 1.0506 47.5
5 Methanol 2.0 1.0431 47.9
1 Methanol/water 2.0 1.0466 47.7
3 Methanol/water 2.0 1.0486 47.6
5 Methanol/water 2.0 1.0494 47.5
Notes: a 20.5 g of modified silica; 1, 2, 3, 4, 5 adsorption process

The data on lightness (L*) might indicate that on Syloid 244, a* value ranged between
an increase in the amount of any type of silane 2 0.68 for the unmodified silica and +9.40
used for modification was associated with the for the silica modified with 5 parts (by weight)
increased amounts of dye adsorbed on the of U-13 silane in methanol/water. The
surface of the modified silica. Possibly, the corresponding values of b* ranged between
number of sites which were active in +0.48 and 2 32.51. In turn, the pigment
the adsorption increased. The a* and b* obtained by adsorption onto the unmodified
values of the pigments obtained reflected the Aerosil 200 exhibited values of a* ¼ 20:43
quality of their colour. For pigments obtained and b* ¼ 219:22: On the other hand, the
156
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Figure 8 Colorimetric data and disposal extent of Syloid 244 modified with Figure 10 Colorimetric data and disposal extent of Syloid 244 modified with
different parts (by weight) of U-13 silane (in methanol/water) after different parts (by weight) of U-13 silane (in methanol) after adsorption of
adsorption of C.I. Reactive Blue 19 C.I. Acid Green 16

Figure 9 Colorimetric data and disposal extent of Aerosil 200 modified with Figure 11 Colorimetric data and disposal extent of Aerosil 200 modified with
different parts (by weight) of U-15 silane (in water) after adsorption of C.I. different parts (by weight) of U-15 silane (in methanol) after adsorption of
Reactive Blue 19 C.I. Acid Green 16

pigment obtained on a silica modified with the modifier applied resulted in more
5 parts (by weight) in water exhibited an a* colourful pigments (of higher a* and b*
value of +7.94 and a b* value of 2 25.15. values).
The data fully correlated with the Similar relations were noted for the
efficiencies of adsorption (Tables II and III, pigments obtained by the adsorption of the
Figures 8 and 9). The graphs indicated C.I. Acid Green 16 dye (Figures 10 and 11).
that the modification resulted in a higher Comparing the results obtained, it can
adsorption efficiency which, in turn, be concluded that the highest lightness
induced a decrease in the lightness of ðL* ¼ 97:46Þ was given by the pigment
the obtained pigments and an increase in obtained by adsorption on the unmodified
the colorimetric parameters, in this case, Syloid 244, while the lowest lightness
in the very significant b* value, corresponding ðL* ¼ 55:81Þ was demonstrated by the
to blue colour. pigment obtained by adsorption onto
The above results could be summed up by the the silica modified with 5 parts by weight
conclusion that an increase in the amount of of U-13 silane in methanol. The pigment
157
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

derived from the unmodified silica exhibited Stability of the pigments prepared
an a* value of 2 3.14 and the pigment derived Analysis of the organic dye elution
from silica modified with 5 parts by weight demonstrated that the most stable pigments
of U-13 silane in methanol showed an a* value were those obtained using C.I. Reactive Blue
of 2 36.31. The a* value increased as the 19 (Table V), independent of the type of
amounts of a modifier used was increased, silane. This indicated that strong chemical
resulting in an increased amount of dye bonds had been formed between the modified
adsorbed on the surface of the silica carriers. silica surface and the dye molecules. The least
The lowest b* value was associated with the favourable results were associated with the
pigment derived from the unmodified silica pigments obtained by adsorption of C.I. Acid
ðb* ¼ 20:10Þ and the highest b* value Green 16 on silica modified with 3 parts by
(2 9.16) was given by the pigment derived weight of U-13 silane (methanol/water) or of
from the silica modified with 5 parts by weight U-15 silane (methanol). The fraction of
of U-13 silane in methanol. Similar relations eluted dye was 11.3-12.2 per cent and
were noted in the case of the Aerosil 200 silica. 10.1-14.1 per cent, respectively.

Adsorption characteristics of the

modified silica and pigments prepared Conclusions
As can be seen from Table IV, the unmodified
Syloid 244 showed a specific surface area of Based on the discussions given above, the
333.5 m2/g, a micropore area of 34.7 m2/g and following conclusions could be made. SEM
a mean pore diameter of 164.2 Å. examination of Aerosil 200 and Syloid 244
Modification with aminosilane in methanol/ showed that the dye adsorption on the
water (4:1) caused a decrease in the specific modified silica carrier resulted in a highly
surface area and in the micropore surface uniform pigment. Dye adsorption on the
while increasing the mean pore diameter modified Syloid 244 prevented the formation
(to 195.6 Å). The pigment obtained by the of agglomerate. The analysis of the particle
adsorption of C.I. Reactive Blue 19 organic size distribution revealed that the highly
dye on the silica surface showed the lowest uniform pigments could be obtained using
specific surface area. A decrease in the specific Syloid 244 as a core. On the other hand,
surface area may be due to the blocking of the binding of Aerosil 200 with dyes resulted in
active centres both by the modification of the particles of smaller diameters.
silica surface with the organofunctional silane Modification of silica with silanes clearly
and by the adsorption of the organic dye. increased the silica’s efficiency of adsorbing
The unmodified Aerosil 200 had a specific C.I. Reactive Blue 19 and C.I. Acid Green
surface area of 178.1 m2/g, a micropore area 16 dyes. In particular, high adsorption
of 0.9 m2/g and a mean pore diameter of efficiencies were noted for silica modified with
81.2 Å (Table IV). Modification of the silica 5 parts by weight of U-13, U-15 and U-17
with 3 parts by weight of U-15 silane, carried silanes.
out in methanol/water (4:1), caused an Surface modification enabled silica carrier
increase in the specific surface area to be used as a core for the production of
(to 193.5 m2/g). The surface area of the pores pigments of reduced lightness. On the other
also increased while the mean pore diameter hand, an increase in other colorimetric
decreased. Binding of the organic dye C.I. parameters, in particular the values of the +b*
Reactive Blue 19 resulted in a decrease of the value corresponding to the blue colour and
specific surface area (to 140.6 m2/g). the 2 a* value corresponding to the green

Table IV Specific surface area, micropore area and average pore diameter of the samples prepared
Specific surface area Micropore area Average pore diameter
Sample (m2/g) (m2/g) (Å)
Syloid 244 333.5 34.66 164.23
Syloid 244+3U-15(m/w) 288.5 23.71 195.65
Syloid 244+3U-15(m/w)+RB19 273.4 26.09 167.54
Aerosil 200 178.1 0.86 81.23
Aerosil 200+3U-15(m/w) 193.5 2.55 71.88

158
 Properties of amorphous silica Pigment & Resin Technology
A. Krysztafkiewicz, S. Binkowski, A. Kaczmarek and T. Jesionowski Volume 32 · Number 3 · 2003 · 149–159

Table V Elution of the organic dyes adsorbed on silica surface

Dyes concentration Amount of dyes eluted from
Pigment sample Modification medium after elution (mg/cm3) silica surface (per cent)
Syloid244+3U-17+RBa Methanol/water 0.0 0.0
Syloid244+3U-17+RBb Methanol/water 0.0 0.0
Syloid244+3U-17+RBc Methanol/water 0.0 0.0
Syloid244+3U-17+RBd Methanol/water 0.0 0.0
Syloid244+3U-17+RBe Methanol/water 0.0 0.0
Syloid244+3U-17+RBf Methanol/water 0.0 0.0
Syloid244+3U-15+RBb Methanol/water 0.0 0.0
Syloid244+3U-15+RBe Methanol/water 0.0 0.0
Syloid244+3U-13+RBb Methanol/water 0.0 0.0
Syloid244+3U-13+RBe Methanol/water 0.0 0.0
Syloid244+3U-15+AGb Methanol 0.02970 10.08
Syloid244+3U-15+AGe Methanol 0.04145 14.06
Syloid244+3U-13+AGb Methanol/water 0.03344 11.33
Syloid244+3U-13+AGe Methanol/water 0.03595 12.18
Aerosil 200+3U-15+AGb Methanol/water 0.10399 10.93
Aerosil 200+3U-15+AGe Methanol/water 0.10867 11.42
Notes: a30 min at room temperature; b60 min at room temperature; c180 min at room temperature; d30 min at 1008C
temperature; e60 min at 1008C temperature; f180 min at 1008C temperature

colour. An increase in the amount of the Giesche, H. and Matijevic, E. (1991), “Well-defined
modifier used resulted in pigments of a higher pigments I. Monodispersed silica-acid dyes
systems”, Dyes and Pigments, Vol. 17 No. 4, p. 323.
colour strength (increased values of a* and
Guthrie, J.T. and Kunaver, M. (1997), “The characterisation
b*). Values of organic dye elution evidently and the application of modified pigmented
showed that the most stable pigments were systems”, Surface Coatings International, Vol. 80
those derived from the adsorption of C.I. No. 9, p. 427.
Reactive Blue 19 dye. Hsu, W.P., Yu, R. and Matijevic, E. (1992), “Well-defined
colloidal pigments II. Monodispersed inorganic
spherical particles containing organic dyes”, Dyes
and Pigments, Vol. 19 No. 3, p. 179.
References Krysztafkiewicz, A., Jesionowski, T. and Binkowski, S.
(2000), “Precipitated silica modified with
Aiken, B., Hsu, W.P. and Matijevic, E. (1988), “Preparation 3-aminopropyltriethoxysilane”, Colloids and
and properties of monodispersed colloidal particles Surfaces, A: Physicochemical and Engineering
of lanthanide compounds: III. Yttrium(III) and mixed Aspects, Vol. 173 Nos. 1-3, p. 73.
yttrium(III)/cerium(III) systems”, Journal of the Lambourne, R.; Strivens, T.A. (Eds) (1999), Paint and
American Ceramic Society, Vol. 71 No. 10, p. 845. Surface Coatings-Theory and Practice, 2nd ed.,
Binkowski, S. and Krysztafkiewicz, A. (2002), p. 950.
“Physicochemical properties of organic pigments on Matijevic, E. (1998), “Preparation and characterisation of
a silica core”, Pigment and Resin Technology, Vol. 31 well defined powders and their applications in
No. 2, p. 96. technology”, Journal of the European Ceramic
Binkowski, S., Jesionowski, T. and Krysztafkiewicz, A. Society, Vol. 18 No. 9, p. 1357.
(2000), “Preparation of pigments on modified Tentorio, A., Matijevic, E. and Kratohvil, J.P. (1980),
precipitated silica”, Dyes and Pigments, Vol. 47 “Preparation and optical properties of spherical
No. 3, p. 247. colloidal aluminum hydroxide particles containing a
Carter, S. and Bristow, D. (1998), “New applications for dye”, Journal of Colloid and Interface Science, Vol. 77
age old pigments”, Paint and Ink International, No. 2, p. 418.
Vol. 11 No. 4, p. 15. Winnik, F.M., Keoshkerian, B., Fuller, J.R. and Hofstra, P.G.
Christie, R.M. (2001), Colour Chemistry, Royal Society of (1990), “New water-dispersible silica-based
Chemistry, Cambridge. pigments: synthesis and characterization”, Dyes and
Galgoci, E.C., Komar, P.C. and Elmore, J.D. (1999), “High Pigments, Vol. 14 No. 2, p. 101.
performance waterborne coatings based on Wu, G., Koliadima, A., Her, Y.-S. and Matijevic, E. (1997),
dispersions of a solid epoxy resin and an “Adsorption of dyes on nanosize modified silica
amine-functional curing agent”, Journal of Coatings particles”, Journal of Colloid and Interface Science,
Technology, Vol. 71 No. 891, p. 45. Vol. 195 No. 1, p. 222.

159