Materials Science and Engineering B106 (2004) 5255

The study of formation colloidal silica via sodium silicate

Ming-Shyong Tsai
The Department of Chemical Engineering, Southern Taiwan University of Technology, Tainan, Taiwan, ROC

Received 17 June 2003; accepted 28 August 2003

Abstract

The process parameters of the formation colloidal silica via sodium silicate had been investigated in this article. Sodium ion of sodium
silicate was removed by ion-exchanging to obtain the active silicic acid which was titrated to the solution of potassium hydroxide (KOH) to
form the colloidal silica. In this study, the results showed the mean particle size of colloidal silica was influenced by the KOH concentration,
formation temperature and titration rate of active silicic acid. High KOH concentration, high formation temperature and low titration rate of
active silicic acid would help the particle growth to form the larger particle size of colloidal silica. Unfortunately, the colloidal silica formed
at theses conditions were unstable.
2003 Elsevier B.V. All rights reserved.

Keywords: Colloidal silica; Sodium silica; Particle formation

1. Introduction
The formation process of colloidal silica was an old nano
technique since 19th century [19]. The colloidal silica had
been applied in the fields of making paper [10] and model
for casting. Recently, it has been applied in the modern in-
dustries, such as binder in inorganic paint, stiffener in hard
coating reagent [1115] and especially as an abrasive parti-
cle of chemical mechanical polishing slurry [1618]. There
were several commercial CMP slurries using colloidal silica
as a raw material. The high purity and large particle size of
colloidal silica is need for the application in CMP slurry.
Many commercial products already made by colloidal silica,
but only few literatures had discussed about this process.
Stober and Rang [2] used tetraesters and ammonia as the
raw materials which reacted in alcohol solution to form the
monodisperse silica in the macron size range. Chen et al.
[3] studied the new particle formation in the monosize silica
seeds who used Si(OH)4 from TEOS hydrolysis as the raw
material. Chen indicated that the new particles are formed in
the certain condition: the early stage of growth of silica par-
ticles are controlled by diffusion of condense species, have
electric charge against an electrostatic repulsion, onto the
Tel.: +886-6-2533131; fax: +886-6-2425741.
E-mail address: tsaims@mail.stut.edu.tw (M.-S. Tsai).
surface of surface of silica seeds. Coenen and Kruif [4] used
Stober process but used commercial Ludox as the seeds to
synthesis and growth the colloidal silica particles. Yoshida
[1] indicated that the processes used for making colloidal
silica from sodium silicate included peptization method,
acid-neutralization method and ion-exchanging method. The
ion-exchange method was controlled more easily than the
other methods. The homogenous nucleation and the surface
growth played important roles in the mechanisms of particle
formation via ion-exchange method. In this study, the pro-
cess parameters to control the particle size and the stability
of colloidal silica such as forming temperature, alkali con-
centration and titration rate of active silicic acid had been
discussed.
2. Experimental
One hundred and forty grams of sodium silicate (commer-
cial) were diluted with water to 1000 ml. The active silicic
acid was made by passing that diluted sodium silicate solu-
tion through a column where filled with about 3 l cation ex-
change resin (Amberlite 120, pH = 2.3). The sodium ion of
the dilute sodium silicate solution was substituted by hydro-
gen ion on the exchange sites of cation resin. The active sili-
cic acid was a specific gravity 1.02 g/cm3 which contained

0921-5107/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2003.08.052
 M.-S. Tsai / Materials Science and Engineering B106 (2004) 5255
Diluted water DI water + KOH
Cation exchange Heating
Active silicic acid KOH solution
Colloidal silica
PSD, Zeta potential, TEM
and accelerate aging test
Fig. 1. The experimental flowchart of formation colloidal silica.
about 3.6 wt.% of Si(OH)4 that was calculated by assuming
the solution was a mixing density of silica (specific gravity
was 2.2 g/cm3 ) and water (specific gravity was 1 g/cm3 ). A
100 ml de-ionic water with 5, 10 and 15 g potassium hydrox-
ide (KOH) (E Merck) was heated to the desire temperatures
(at 60, 80 and 100 C, respectively). The active silicic acid
was titrated to the KOH solution with a constant flow rate
which was controlled by peristaltic pump. The experimen-
tal flow chart and the experimental apparatus are shown in
Figs. 1 and 2, respectively.
The formed products were characterized by particle size
distribution, zeta potential (Malvern Zetasizer 3000HSA),
TEM and accelerated aging test. The stability of colloidal
silica is very important in its application. The accelerated
aging test can be taken by decreasing the slurry pH value and
increasing the store temperature. The potassium ion were
removed from the products and pH value from 1011 to 23
by mixing with cation exchange resin changed itself and
then separated it. The acidified slurries were placing in the
oven at 65 C for 7 days. When the slurry did not gel in
the accelerated aging test, the case was identified as stable;
otherwise it was unstable if it gelled in the accelerated aging
test.
Fig. 2. The experimental apparatus of formation colloidal silica.
53
60
50 60C
Mean particle size(nm) .
80C
40 100C
30
20
10
0
0 0.5 1 1.5 2
KOH (wt%)
Fig. 3. The influence of the KOH concentration to the mean particle sizes
of colloidal silica as titrated with 10 ml/min.
3. Results and discussion
During particle formation, the homogenous nucleation of
active silicic acid was occurred first which was the seed in
the KOH solution of following titration. The surface growth
became important as the active silicic acid was continuous
titrated to the solution with the new born seed. As titrat-
ing with the quick rate such as 10 ml/min, the influence of
formation temperature and KOH concentration to the mean
particle size of colloidal silica is shown in Fig. 3. The mean
particle size of colloidal silica was not change obviously
as the formation temperature below 80 C. But the parti-
cle size was increasing at 100 C in KOH concentration
above 1 wt.%. Increasing the KOH concentration, the elec-
trical conductivity of the solution would increase. The ex-
tra electrolyte in the solution compressed the thickness of
electrical double layer on the colloidal silica which made
the particle growth more easily. The lower formation tem-
perature and lower KOH concentration seem not benefic the
particle growth. In the Fig. 3, the colloidal silica formed at
60 C seems to be slight larger than that formed at 80 C.
Fig. 4 shows the morphologies of colloidal silica which
were formed at various temperatures. Many nano grade and
spherical bubbles were traped in the small colloidal silica
aggregation which can be observed in Fig. 4(a). The serious
agglomerate was occurred between small particles at 60 C.
The nano size and spherical colloidal silica was formed and
could be distinct each others as the formation temperature
above 80 C as shown in Fig. 4(b) and (c). Fig. 5 shows the
mean particle size of colloidal silica formed at various tem-
peratures in which the active silicic acid was titrated with
the slow rate (5 ml/min). The mean particle size of colloidal
silica was increased by increasing the formation tempera-
ture or increasing the concentration of KOH, which similar
to the cases with the quick rate of titration. As compar-
ing between Figs. 4 and 5, the mean particle size of col-
loidal silica formed by slow titrated rate were general larger
than that formed by the quick titrated rate. It was probably
54 M.-S. Tsai / Materials Science and Engineering B106 (2004) 5255

Fig. 4. The morphology of colloidal silica formed in 1 wt.% KOH solution at (a) 60 C; (b) 80 C; (c) 100 C as titrated with 10 ml/min.

caused by the time difference between the surface growth

and titration. If titration rate is faster than the surface growth,
60 the adding active silicic acid might not have enough time
60C to consume itself on the surface of seed. It would induce
50 the accumulation concentration of active silicic acid, and
80C
Mean particle size(nm)

100C
then the homogenous nucleation occurred. The colloidal sil-
40 ica formed at this condition was small particle size. Oth-
erwise, if titration rate is slower than the surface growth,
30 the time of surface growth seems to be enough. The sur-
face growth would dominate the mechanism of particle for-
20
mation. The large particle of colloidal silica could be made
in the condition of high KOH concentration at high forma-
10
tion temperature. Unfortunately, the colloidal silica might
aggregate and became unstable at this condition. Table 1
0
0 0.5 1 1.5 2 shows the forming condition and the stability of colloidal
silica. The colloidal silica formed in the solution of high
KOH (wt%)
KOH (1.5 wt.%) concentration was gelled in the accelera-
Fig. 5. The influence of the KOH concentration on the mean particle tion aging test at all formation temperatures. The colloidal
sizes of colloidal silica as titrated with 5 ml/min. silica formed at 100 C in 1 wt.% KOH also gelled in the
 M.-S. Tsai / Materials Science and Engineering B106 (2004) 5255 55

Table 1
The effect of formation conditions on the stability of colloidal silica
Titration rate KOH (wt.%) 5 ml/min 10 ml/min

60 C 80 C 100 C 60 C 80 C 100 C

0.5 Stable Stable Stable Stable Stable Stable

1 Stable Stable Unstable Stable Stable Unstable
1.5 Unstable Unstable Unstable Unstable Unstable Unstable

40 4. Conclusion

The process parameters of the formation colloidal sil-

20
ica via sodium silicate had been investigated. The results
Zeta potential ( mv ) .

showed that the process parameters such as the titration rate,

0 the KOH concentration and the formation temperature have
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 influences on the mean particle size of colloidal silica. The
-20 mean particle size of colloidal silica increased with increas-
ing KOH concentration, increasing formation temperature
-40 and decreasing the titration rate of active silicic acid. Unfor-
tunately, the colloidal silica formed at these conditions were
unstable in accelerate aging test. The formed colloidal silica
-60
had an IEP at pH of about 2.

-80
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-100
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