COLLOIDS

Colloids and Surfaces

AND
SURFACES
A
ELS EV IER A: Physicochemicaland EngineeringAspects 132 (1998) 45-52

Preparation and characterization of ultrafine silica

Sridhar Sadasivan a, D o n H. Rasmussen a'*, Freeman P. Chen b, R.K. Kannabiran b
a Department of Chemical Engineering, Center for Advanced Materials Processing, Clarkson University, Potsdam,
NY13699, USA
b Polaroid Corporation, Waltham, MA 02154, USA
Received 31 October 1996; accepted 2 April 1997

Abstract

Silica dispersions of size ranging from 20-60 nm with solid content ranging from 1 2 wt.% were prepared by
hydrolysis followed by condensation of TEOS in methanol. Aqueous dispersions were prepared by adding appropriate
amounts of water to the dispersion and removing the methanol by vacuum distillation in a rotary evaporator. The
solid contents of the aqueous dispersions varied between 5 and 7 wt.%. These dispersions were produced for use as
model colloids in thin-film coating experiments. The dispersions were characterized by dynamic light scattering, gel
permeation chromatography and zeta potential measurements. 1998 Elsevier Science B.V.

Keywords: Dynamic light scattering; Gel permeation chromatography; Silica; Zeta potential

1. Introduction applications. They are used to make electronic

Nanometer-sized concentrated aqueous
dispersions of silica are commercially prepared by
acidification of aqueous solutions of sodium sili-
cate made from sand [1]. Upon acidification at
high temperature, supersaturated solutions of
silicic acid are formed. Supersaturated silicic acid
solutions in pure water are thermodynamically
unstable, because condensation polymerization
through dehydrolysis occurs leading to the forma-
tion of small nuclei. These nuclei grow until the
particles are colloidally stable. These natural
sodium silicates contain a certain amount of alumi-
num as a contaminant, which is incorporated in
the silica particles. The dilute suspensions of silica
are then concentrated in an evaporator to form
concentrated sols with weight fractions up to 30%.
Aqueous silica dispersions have many different
* Corresponding author. E-mail: rasmu@sun.soe.clarkson.edu
substrates, thin film substrates, electrical insula-
tors, thermal insulators, humidity sensors, organic
catalysts, etc. The silica particles play a different
role in each of these products. The quality of some
of these products is highly dependent on the charge
and size of the silica particles. Commercial silicas
have a broad size distribution and varying levels
of metal contaminants. It is imperative to have
silica particles of narrow distribution and high
purity to conduct model studies.
Stober et al. [2] first prepared monodisperse
silica particles from silicon alkoxides and demon-
strated that control over the size and size distribu-
tion can be achieved. This chemical synthesis
technique also provides particles of high purity.
Bogush and Zukoski [3] have done extensive work
on the preparation of silica powders from tetra-
ethyl orthosilicate (TEOS). They prepared mono-
disperse particles having sizes ranging from 40 nm
to several micrometers by controlled hydrolysis of

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46 S. Sadasivan et al. / Colloids Surj;tees A." Physicochem. Eng. Aspects 132 (1998) 45 52
TEOS in ethanol, followed by condensation of the
dispersed phase material. The two reactions which
describe the hydrolysis and condensation of
tetraalkoxy silicate in alcohol are:
Si (OR)4 + 4H20 ~ Si (OH)4 + 4 R O H
Si (OH)4--* SiO2 + 4H20
Hydrolysis is a very slow reaction. Either an
acid or a base is used as a catalyst. Gel structures
are obtained in the presence of acid, while the
base, usually ammonia, acts as a morphological
catalyst producing spherical particles. Five primary
factors were found to affect the ultimate size of
the silica particles. They were: (1) concentration
of TEOS; (2) concentration of ammonia; (3) con-
centration of water; (4) alcohol used as the solvent;
(5) reaction temperature.
Bogush and Zukoski [3] observed that, for a
particular concentration of TEOS with ethanol as
solvent, particle size goes through a maximum as
both ammonia and water concentrations are
increased. Similar behavior was observed for all
the TEOS concentrations studied, but the maxi-
mum moved to higher ammonia and water concen-
trations as the TEOS concentration increased. The
maximum achievable monodisperse size by this
process was found to be 0.8 gm. While narrow size
distributions were achievable by this process, the
solid content of the resulting dispersion was less
than 2 wt.%. Attempts to increase solid content by
simply increasing the initial TEOS concentration
for a particular concentration of ammonia and
water resulted in larger particle sizes and broader
particle size distributions.
For different alcohols used as solvents, Harris
et al. [4] found that the final particle sizes obtained
under comparable conditions were smallest in
methanol and increased with increase in the carbon
chain length of the alcohol. The particle size was
also found to increase as the alcohol was changed
from primary to tertiary. The particle size distribu-
tion varied from a narrow to a broader one as the
alcohol molecular weight was increased.
The effect of reaction temperature on final par-
ticle properties has been explored over the range
from - 2 0 to +55C by Tan et al. [5]. The final
size of the particles decreased with increase in
temperature. While monodisperse particles were
not obtained at lower temperatures, very narrow
size distributions were obtained at elevated
temperatures.
The main aim of this work is to prepare aqueous
( 1) dispersions of silica particles having sizes ranging
(2) from 20 6 0 n m with a solid content of about
5 wt.%. With ethanol as the solvent, a very low
concentration of water is required to achieve this
size and results in dispersions with solid contents
less than 1 wt.%. Here we present the results from
a series of experiments in which methanol was
used as the solvent and moderate concentrations
of ammonia and water were needed to produce
dispersions of the required size and maximum
achievable solid content.
2. Experimental details
2.1. Reagents
TEOS (99.9+% pure Aldrich), ammonium
hydroxide (99.9+% pure Aldrich) as a 30%
solution in water and spectrophotometric grade
methanol (99.9+% pure Aldrich) were used
as-purchased.
2.2. Preparation of silica
Typically, a round-bottomed glass flask
immersed in a constant-temperature bath main-
tained at the required temperature (20 to 35C)
was used as the reaction vessel. The glass flask
was cleaned with deionized water and rinsed with
deionized water several times prior to the experi-
ment. For each experiment, the required amount
of methanol and ammonium hydroxide were added
to the reaction vessel and a slow to moderate
mixing speed was established with a propeller
shaft. The reaction was initiated by adding the
desired amount of TEOS to the mixture of ammo-
nium hydroxide and methanol. Upon addition of
TEOS, the reaction mixture remained clear for
some time. Slowly, the mixture became turbid due
to the formation of silica. The reaction was com-
plete in 1-2 h. The solid content of the final
dispersion varied from 1.5 to 2.0 wt.%. The solid
 S. Sadasivanet al. / ColloidsSurfaces A: Physicoehem. Eng. Aspects 132 (1998) 45-52
content of the dispersion was determined from
the amount of residual solids after solvent
evaporation.
2.3. Preparation of aqueous dispersion
A concentrated aqueous dispersion of silica was
prepared from the methanol dispersion by adding
an appropriate amount of water and evaporating
the methanol and ammonia under vacuum from
the methanol/water dispersion. Methanol distills
under vacuum at room temperature. It does not
form an azeotrope with water under the conditions
used in this work. The final aqueous dispersion
contained 5 to 7 wt.% silica. The solids content
was determined from the residual solids after
solvent evaporation. The residual methanol in the
aqueous dispersion was determined by gas chroma-
tography. The aqueous dispersion was centrifuged
and the supernatant was used for the gas chroma-
tographic experiment. The residual methanol
content in the dispersion was found to be less than
1 vol.%. The amount of residual ammonia in the
dispersion was not quantified.
2.4. Characterization techniques--size analysis
Particle size distributions were determined by
dynamic light scattering (DLS) and gel permeation
chromatography (GPC).
2.4.1. D L S [61
DLS measures the diffusion coefficient of the
particles which are undergoing Brownian motion
in the dilute suspension. In this technique, the
sample is irradiated with a monochromatic beam
of laser light and the light scattered from the
dispersion is collected by a photodetector. This
technique involves measuring the scattered light
intensity at a certain instant of time and comparing
it with the intensity obtained at a later time, i.e.
the correlation between the intensity fluctuations
of scattered light at different time intervals is
monitored. The measurements are taken at time
intervals which are short compared with the time
for diffusion, because there is a very good correla-
tion during initial times which gradually disappears
as time increases. The measured autocorrelation
47
function of the intensity of the scattered light
g2(r) can be related to the diffusion coefficient by
g2(z) = 1 +fl exp(- 2Doq2~) (3)
where fl is an experimental constant, Do is the free
particle diffusion coefficient, r the sampling time
and q is the scattering vector given by
4rcn
q= sin(0/2) (4)
"~o
where n is the refractive index of the medium, 0 is
the scattering angle and 2o is the wavelength of
the laser light in vacuum. The free particle diffusion
coefficient Do is related to the particle diameter d
by the Stokes-Einstein relationship
kBT
D0 - (5)
3rcqd
where k~ is the Boltzmann constant, T the temper-
ature and q the viscosity of the suspending
medium. In many cases, the sample might contain
particles of different sizes. In all such cases, the
autocorrelation function measured is the weighted
sum of all individual contributions to the dynamics
of the scattered light.
DLS experiments were performed using a
Brookhaven light scattering instrument. The light
source is an air-cooled argon-ion laser which pro-
duces monochromatic radiation of wavelength
514 nm. The laser beam is focused on the sample
cell by means of a lens assembly. The sample cell
is located in the middle of a temperature-controlled
bath with trans-decalin as the refractive index
matching fluid. The transmitted light is detected
by means of a photomultiplier tube (PMT). The
PMT and the sample cell are mounted on a
goniometer arrangement. A stepper motor is used
to change the angle of the PMT. The PMT converts
the photons into pulses which are then counted
and processed by a BI2030AT Brookhaven correla-
tor. The correlator is interfaced with a computer
which is used to collect and process the auto-
correlation functions.
Typically, the autocorrelation functions can be
analyzed by different techniques like cumulants
analysis, non-negative least squares analysis and
constrained regularization analysis [7]. Depending
48 s. Sadasivan et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 132 (1998) 45-52
upon the technique used, either an average size or
a size distribution can be obtained. The size distri-
bution could be ambiguous due to the ill-condi-
tioned nature of the analyzing problem, i.e. in the
presence of experimental noise, for a particular
autocorrelation function a whole series of solutions
may exist within the range of experimental error.
For a given experiment the individual solutions
may be very different from one another; hence, an
uncertainty is associated with the selection of any
of those solutions as the best estimate. The second-
order cumulants analysis was used to obtain an
average particle size in all the experiments
reported here.
The samples for the DLS experiments were
prepared by diluting several drops of the concen-
trated silica dispersion with phosphate buffer solu-
tion (containing 10 mM sodium dibasic phosphate,
2% sodium azide, pH adjusted to 6.8 with
phosphoric acid). The samples were then filtered
through a 0.2 tam acrodisc filter. The concentration
of silica in the final dispersion varied between 2
and 3 mg ml - 1. The concentration was determined
from the residual solids after solvent evaporation.
2.4.2. G P C
GPC is traditionally used as a technique for
determining the molecular weight distribution of
polymers. The separation of polymers in the gel
permeation chromatography is based on a size
exclusion mechanism, i.e. polymers separate based
on their hydrodynamic volume. Fischer and
coworkers [8,9] have used this technique to deter-
mine the size distribution of nanometer-sized gold
particles and colloidal cadmium sulfide particles.
G o o d separations between different sized particles
were achieved. By examining the GPC fractions
under an electron microscope, size distribution of
the particles were calculated.
Chen et al. [10] have modified the GPC tech-
nique [ 1 l] to allow a quantitative determination
of the size distribution of nanometer-sized silica
particles. It was shown that water soluble pullulans
are suitably sized references to calibrate the GPC
system, i.e. to convert retention volumes to particle
dimensions. We characterized the size distribution
of our silica dispersions by this technique.
All GPC experiments were done with a 10 mM
solution of dibasic sodium phosphate salt also
containing 2 wt.% sodium azide in deionized water
adjusted to a final pH of 6.8 with phosphoric acid.
The solution was filtered through a 0.2 lam acrodisc
filter and then degassed to remove any dissolved
air. The experimental set-up consisted of two
AsahiPak columns in tandem (GFA-30F and
GFA-50F), both containing a vinyl copolymer gel
with an average particle size of about 5 ~tm. The
column and the guard column were maintained at
40C. A Wisp 710 Auto sampler was used for
injecting the samples while a Waters 590 pump
was used for eluent delivery. The pump was oper-
ated at 0.5 m l m i n 1. Typical injection volumes
were 50 ~tl of the sample. The eluent from the
column was divided exactly into two equivalent
volume streams to accommodate the two detectors.
The first flow path was connected to a Waters 410
differential refractometer. The second flow path
was connected to a H502B viscometric detector.
The signal from the refractometer is directly pro-
portional to the concentration of the material
eluted. The viscometer signal, which corresponds
to the pressure drop during elution, is related to
the concentration of the material times its intrinsic
viscosity. A Viskotek data module converts the
410 analog signal into a digital format and it was
collected by a 486 computer under the control of
TRISEC viskotek software. To remove any dis-
solved air which can give rise to extraneous signals,
helium was used to continuously purge the mobile
phase. To correct for any slight variation in the
pump speed, glycerol was added to the silica
dispersion to serve as an internal timing marker.
The average experimental time to acquire data
from a single injection was about 55 rain.
Calibration curves were generated with six
narrow molecular weight pullulan standards. Ono
[11] gives details on the data analysis.
2.4. 3. Electrokinetic analysis." zeta potential
measurements [ 1 2 , 1 3 ]
Electrokinetic analysis was performed to
determine the charge characteristics of the silica
dispersion. A Matec ESA System 8000 was used
to determine the zeta potential of the silica disper-
sions. The electroacoustic effect is observed when
an alternating voltage is applied to a colloid. The
 S. Sadasivan et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 132 (1998) 45-52 49

particles move back and forth, at a velocity Table 1

Experimental conditions and particle diameters obtained from
depending upon the size, charge and frequency of
DLS for different runs
the applied field, and thereby generate sound
waves. Description [TEOS] [NH3] [H20 ] Temp. Diameter
The main component of the ESA system is the (M) (M) (M) (C) (nm)
acoustic cell. The stirred cell contains two parallel
RI 0.15 0.5 2.5 18 59+3
plate electrodes, pH, temperature and conductivity R2 0.18 0.5 2.5 18 65_+5
probes. Computer-controlled burettes are used for R3 0.087 0.5 2.5 18 50_+5
titrant addition. The colloid is contained within R4 0.087 0.5 2.5 25 40_+2
this cell and is surrounded by a water jacket to R5 0.15 0.5 2.5 25 51_+2
PS1 0.10 0.5 2.5 35 28_+1
maintain a constant temperature during the experi-
PS2 0.15 0.5 2.5 35 41 _+3
ment. The electrodes are attached to a pair of glass
blocks. The ESA signal is generated by applying
a pulse of alternating voltage across the electrodes.
The resulting sound waves travel through the glass Table 2
Data for various GPC standards
blocks and are measured by a transducer. The
Fourier transform of the ESA signal is determined. Description Retention Molecular Intrinsic
The average of this quantity over a prescribed volume weight viscosity
number of pulses is stored in a 486 computer. The (ml)
empirical relationship between the experimental PSS-standard 1 12.16 100000 0.384
signal and the properties of the colloidal materials PSS-standard 2 15.31 12200 0.100
in the limit of low volume fraction has been given PSS-standard 3 14.28 23700 0.150
by O'Brien and coworkers [12,13] as PSS-standard 4 11.50 186000 0.626
PSS-standard 5 13.09 48000 0.238
PSS-standard 6 16.55 5800 0.065
S~ =O.Olc~b Ap #@o)Gf (6)

where S/mPa m V-1 is the observed signal, ~ is

the instrument constant (at low volume fraction),
c/m s-1 is the speed of sound in the continuous
phase, Ap/g cm-3 is the density difference between
the particle and the continuous phase,
#(oJ)/gm cm s-1 V -1) the dynamic mobility at fre-
quency ~o/rad s- 1 and ~b the volume fraction. Gf is
the geometrical and acoustic gain factor. In prac-
tice it is convenient to lump ~ and Gf together and
determine this ratio as one instrumental constant.
At higher volume fractions (greater than 0.05)
7/Gf is dependent on the electrode/probe geometry
and on the volume fraction.
The electroacoustic mobility or dynamic mobil-
ity #@o) is related to electrophoretic mobility #(0)
as described by O'Brien and coworkers, and is
given by
#(~o) =/~(0)G = ~-q (1 +f)G
where G represents the effect of inertial forces on
the dynamic mobility. Here a is the particle radius,
e the permittivity of the liquid, ~/ the dynamic
viscosity, v the kinematic viscosity, and f the field
factor. For very small values of a, i.e. a < 100 nm,
G~ 1, and hence the inertial forces are unimport-
ant. In such cases, it is possible to determine the
zeta potential directly from the mobility measured
at a single frequency. For all the experiments
described in this paper #(e~)= #(0). The field factor
f = 1 was used and the synthesizer frequency was
set at 1 MHz. 1.25 wt.% silica dispersions were
used to perform all the experiments.
3. Results and discussion
The concentrations of TEOS, ammonia and
water, the reaction temperature and the mean
(7)
particle size measured by DLS are shown in
Table 1. These experiments were all performed
with methanol as the solvent. For each run shown
50 S Sadasivan et aL / Colloids Surfaces A: Physicochem. Eng. Aspects 132 (1998) 45 52
in Table 1, the DLS experiments were repeated five
times and the reported size is the average from the
five runs. The deviations between the runs were
less than 5% for all the DLS experimental data
reported here.
When the TEOS concentration is increased for
one particular concentration of ammonia and
water at a given temperature, particle size
increases. This is consistent with the findings of
Bogush and Zukoski [3]. When the temperature is
increased for a given concentration of TEOS,
ammonia and water, the particle size decreases, as
observed by Tan et al. [5].
The solid content of the resulting methanol
dispersions varied from 1.25 to 1.5 wt.% for most
of the dispersions, except for R3 and R4 where
the solid content was around 1 wt.%. The light
scattering experiments were performed on both
dispersions in methanol and water and the same
particle size was observed. Concentrated aqueous
dispersions of silica were prepared by adding
appropriate quantities of water and then vacuum
distilling to remove the methanol. The solid
content of the final dispersions varied from 5
to 7 wt.%.
GPC experiments were performed on the con-
centrated aqueous dispersions. A calibration curve
7.5
7.0-
6.0.
5.5.
112 ,13 |14 11.~ 16
Relentiocl V ~ u m ~ (ml)
Fig. 1. Calibration curve for the GPC experiments. Vh is the
product of molecular weight and intrinsic viscosity. The curve
is a third-order least squares polynomial fit to the data points.
was used to convert the retention volume values
of the silica samples to corresponding viscometric
radius values. The intrinsic viscosities and reten-
tion volumes for the pullulan standards are given
in Table 2. The logarithms of intrinsic viscosity
multiplied by molecular weight vs. retention
volume were plotted to obtain the calibration curve
shown in Fig. 1. The curve which best fits the data
was a third-order polynomial. The curves in Fig. 2
show the retention volume vs. normalized
concentration values for the silica samples. After
converting the retention volume values into the
corresponding viscometric radius values, the nor-
malized concentration-viscometric radius plots for
all the silica samples are shown in Fig. 3. To
compare the results from the dynamic light scatter-
ing experiments and the GPC experiments, z-
average values were calculated. The expression for
the z-average diameter is given by [14]
2 (Wi/d31)
dz - i (8)
(w,/d:)
i
where wi is the weight fraction of particles with
the viscometric diameter d. From Table 3, a reason-
able agreement between the z-average diameter
value from GPC experiments with the diameter
value obtained from the DLS measurements can
L0 ~ ~ 8oe
, ', I:::H
.,
17
...., "~', ,,, ,'~ ,~ ,', ,', ,, -
R~ention Volume(ml)
Fig. 2. Normalized concentration vs. retention volume curves
for the various silica samples.
 X Sadasivan et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 132 (1998) 45-52 51

1.1 I I I I I ! [ I I I I ' I

1~2

,D R3

# .,I ~;~,':,~ : .~.,o11

I ,V ~ / . : , ~ o~,;~- ",

I l~' X ~ ~,~ -~ . . . . .
,~o , , . ,~. +'("~/~. , ""'~. z , 6 s ,o
o to lo so 4o pH
R (m)

Fig. 3. Normalized concentration vs. viscometric radius curves Fig. 4. Variation of zeta potential with pH for the different silica
for different silica samples, samples. The discontinuity at point of zero charge is an artifact
of the technique used.

4. Conclusions
Table 3
Comparison of z-average diameter values from GPC experi-
ments and diameter values from DLS experiments for Aqueous dispersions, of silica particles having
different runs sizes ranging from 30-60 nm were prepared by
hydrolysis and condensation of TEOS in methanol
Description z-averageGPC diameter DLS diameter followed by vacuum distilling the methanol. DLS
(nm) (nm) and G P C techniques were used to characterize the
R1 52_+7 59+3 size of the silica dispersions, while zeta potential
R2 64+8 65+5 experiments determined their charge characteris-
R3 50 + 10 50 _ 5 tics. The results have established the G P C tech-
R4 41 +6 40+2 nique as a powerful tool for sizing particles in the
R5 49+6 51 +2
PSI 27 _+7 28 _+1 range of 1-60 nm. The z-average diameter values
PS2 46+ 10 41 +3 calculated from G P C are consistent with the
hydrodynamic diameter values from the DLS
technique. This agreement validates the size
distributions obtained from the G P C technique.
be observed. All the G P C experiments were
repeated and the deviations between the z-average
diameter values from the different runs were Acknowledgment

within 10%.
Fig. 4 shows the variation of the zeta potential This work has been supported by Polaroid
with pH. Similar behavior was observed for all the Corporation as a summer internship for SS. The
samples. The starting p H value of the dispersions authors acknowledge the support of the entire
varied from 8 to 10. The point of zero charge of polymer physics group of Polaroid Corporation.
the dispersions varied from 2.8 to 3.1, consistent The authors would like to thank A. Shere, J. Mack
with that of pure silica surfaces. The deviation in and R. Conforti for their helpful suggestions. The
the zeta potential values at high values might be authors thank J.C. Day for his help in using the
due to the differing concentration of a m m o n i a in ESA system. The authors thank the anonymous
the dispersions. reviewer for his useful comments.
52 S. Sadasivan et al. /Colloids Surfaces A: Physicochem. Eng. Aspects 132 (1998) 45-52

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