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Colloids and Surfaces

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


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

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

0927-7757/98/$19.00 1998ElsevierScienceB.V. All rights reserved.

PH S0927-7757 (97) 00148-9
46 S. Sadasivan et al. / Colloids Surj;tees A." Physicochem. Eng. Aspects 132 (1998) 45 52

TEOS in ethanol, followed by condensation of the temperature. While monodisperse particles were
dispersed phase material. The two reactions which not obtained at lower temperatures, very narrow
describe the hydrolysis and condensation of size distributions were obtained at elevated
tetraalkoxy silicate in alcohol are: temperatures.
The main aim of this work is to prepare aqueous
Si (OR)4 + 4H20 ~ Si (OH)4 + 4 R O H ( 1) dispersions of silica particles having sizes ranging
Si (OH)4--* SiO2 + 4H20 (2) from 20 6 0 n m with a solid content of about
5 wt.%. With ethanol as the solvent, a very low
Hydrolysis is a very slow reaction. Either an concentration of water is required to achieve this
acid or a base is used as a catalyst. Gel structures size and results in dispersions with solid contents
are obtained in the presence of acid, while the less than 1 wt.%. Here we present the results from
base, usually ammonia, acts as a morphological a series of experiments in which methanol was
catalyst producing spherical particles. Five primary used as the solvent and moderate concentrations
factors were found to affect the ultimate size of of ammonia and water were needed to produce
the silica particles. They were: (1) concentration dispersions of the required size and maximum
of TEOS; (2) concentration of ammonia; (3) con- achievable solid content.
centration of water; (4) alcohol used as the solvent;
(5) reaction temperature.
Bogush and Zukoski [3] observed that, for a 2. Experimental details
particular concentration of TEOS with ethanol as
solvent, particle size goes through a maximum as 2.1. Reagents
both ammonia and water concentrations are
increased. Similar behavior was observed for all TEOS (99.9+% pure Aldrich), ammonium
the TEOS concentrations studied, but the maxi- hydroxide (99.9+% pure Aldrich) as a 30%
mum moved to higher ammonia and water concen- solution in water and spectrophotometric grade
trations as the TEOS concentration increased. The methanol (99.9+% pure Aldrich) were used
maximum achievable monodisperse size by this as-purchased.
process was found to be 0.8 gm. While narrow size
distributions were achievable by this process, the 2.2. Preparation of silica
solid content of the resulting dispersion was less
than 2 wt.%. Attempts to increase solid content by Typically, a round-bottomed glass flask
simply increasing the initial TEOS concentration immersed in a constant-temperature bath main-
for a particular concentration of ammonia and tained at the required temperature (20 to 35C)
water resulted in larger particle sizes and broader was used as the reaction vessel. The glass flask
particle size distributions. was cleaned with deionized water and rinsed with
For different alcohols used as solvents, Harris deionized water several times prior to the experi-
et al. [4] found that the final particle sizes obtained ment. For each experiment, the required amount
under comparable conditions were smallest in of methanol and ammonium hydroxide were added
methanol and increased with increase in the carbon to the reaction vessel and a slow to moderate
chain length of the alcohol. The particle size was mixing speed was established with a propeller
also found to increase as the alcohol was changed shaft. The reaction was initiated by adding the
from primary to tertiary. The particle size distribu- desired amount of TEOS to the mixture of ammo-
tion varied from a narrow to a broader one as the nium hydroxide and methanol. Upon addition of
alcohol molecular weight was increased. TEOS, the reaction mixture remained clear for
The effect of reaction temperature on final par- some time. Slowly, the mixture became turbid due
ticle properties has been explored over the range to the formation of silica. The reaction was com-
from - 2 0 to +55C by Tan et al. [5]. The final plete in 1-2 h. The solid content of the final
size of the particles decreased with increase in dispersion varied from 1.5 to 2.0 wt.%. The solid
S. Sadasivanet al. / ColloidsSurfaces A: Physicoehem. Eng. Aspects 132 (1998) 45-52 47

content of the dispersion was determined from function of the intensity of the scattered light
the amount of residual solids after solvent g2(r) can be related to the diffusion coefficient by
g2(z) = 1 +fl exp(- 2Doq2~) (3)
2.3. Preparation of aqueous dispersion where fl is an experimental constant, Do is the free
particle diffusion coefficient, r the sampling time
A concentrated aqueous dispersion of silica was and q is the scattering vector given by
prepared from the methanol dispersion by adding
an appropriate amount of water and evaporating 4rcn
q= sin(0/2) (4)
the methanol and ammonia under vacuum from "~o
the methanol/water dispersion. Methanol distills
where n is the refractive index of the medium, 0 is
under vacuum at room temperature. It does not
the scattering angle and 2o is the wavelength of
form an azeotrope with water under the conditions
the laser light in vacuum. The free particle diffusion
used in this work. The final aqueous dispersion
coefficient Do is related to the particle diameter d
contained 5 to 7 wt.% silica. The solids content
by the Stokes-Einstein relationship
was determined from the residual solids after
solvent evaporation. The residual methanol in the kBT
aqueous dispersion was determined by gas chroma- D0 - (5)
tography. The aqueous dispersion was centrifuged
and the supernatant was used for the gas chroma- where k~ is the Boltzmann constant, T the temper-
tographic experiment. The residual methanol ature and q the viscosity of the suspending
content in the dispersion was found to be less than medium. In many cases, the sample might contain
1 vol.%. The amount of residual ammonia in the particles of different sizes. In all such cases, the
dispersion was not quantified. autocorrelation function measured is the weighted
sum of all individual contributions to the dynamics
2.4. Characterization techniques--size analysis of the scattered light.
DLS experiments were performed using a
Particle size distributions were determined by Brookhaven light scattering instrument. The light
dynamic light scattering (DLS) and gel permeation source is an air-cooled argon-ion laser which pro-
chromatography (GPC). duces monochromatic radiation of wavelength
514 nm. The laser beam is focused on the sample
2.4.1. D L S [61 cell by means of a lens assembly. The sample cell
DLS measures the diffusion coefficient of the is located in the middle of a temperature-controlled
particles which are undergoing Brownian motion bath with trans-decalin as the refractive index
in the dilute suspension. In this technique, the matching fluid. The transmitted light is detected
sample is irradiated with a monochromatic beam by means of a photomultiplier tube (PMT). The
of laser light and the light scattered from the PMT and the sample cell are mounted on a
dispersion is collected by a photodetector. This goniometer arrangement. A stepper motor is used
technique involves measuring the scattered light to change the angle of the PMT. The PMT converts
intensity at a certain instant of time and comparing the photons into pulses which are then counted
it with the intensity obtained at a later time, i.e. and processed by a BI2030AT Brookhaven correla-
the correlation between the intensity fluctuations tor. The correlator is interfaced with a computer
of scattered light at different time intervals is which is used to collect and process the auto-
monitored. The measurements are taken at time correlation functions.
intervals which are short compared with the time Typically, the autocorrelation functions can be
for diffusion, because there is a very good correla- analyzed by different techniques like cumulants
tion during initial times which gradually disappears analysis, non-negative least squares analysis and
as time increases. The measured autocorrelation 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 solution of dibasic sodium phosphate salt also
a size distribution can be obtained. The size distri- containing 2 wt.% sodium azide in deionized water
bution could be ambiguous due to the ill-condi- adjusted to a final pH of 6.8 with phosphoric acid.
tioned nature of the analyzing problem, i.e. in the The solution was filtered through a 0.2 lam acrodisc
presence of experimental noise, for a particular filter and then degassed to remove any dissolved
autocorrelation function a whole series of solutions air. The experimental set-up consisted of two
may exist within the range of experimental error. AsahiPak columns in tandem (GFA-30F and
For a given experiment the individual solutions GFA-50F), both containing a vinyl copolymer gel
may be very different from one another; hence, an with an average particle size of about 5 ~tm. The
uncertainty is associated with the selection of any column and the guard column were maintained at
of those solutions as the best estimate. The second- 40C. A Wisp 710 Auto sampler was used for
order cumulants analysis was used to obtain an injecting the samples while a Waters 590 pump
average particle size in all the experiments was used for eluent delivery. The pump was oper-
reported here. ated at 0.5 m l m i n 1. Typical injection volumes
The samples for the DLS experiments were were 50 ~tl of the sample. The eluent from the
prepared by diluting several drops of the concen- column was divided exactly into two equivalent
trated silica dispersion with phosphate buffer solu- volume streams to accommodate the two detectors.
tion (containing 10 mM sodium dibasic phosphate, The first flow path was connected to a Waters 410
2% sodium azide, pH adjusted to 6.8 with differential refractometer. The second flow path
phosphoric acid). The samples were then filtered was connected to a H502B viscometric detector.
through a 0.2 tam acrodisc filter. The concentration The signal from the refractometer is directly pro-
of silica in the final dispersion varied between 2 portional to the concentration of the material
and 3 mg ml - 1. The concentration was determined eluted. The viscometer signal, which corresponds
from the residual solids after solvent evaporation. to the pressure drop during elution, is related to
the concentration of the material times its intrinsic
2.4.2. G P C viscosity. A Viskotek data module converts the
GPC is traditionally used as a technique for 410 analog signal into a digital format and it was
determining the molecular weight distribution of collected by a 486 computer under the control of
polymers. The separation of polymers in the gel TRISEC viskotek software. To remove any dis-
permeation chromatography is based on a size solved air which can give rise to extraneous signals,
exclusion mechanism, i.e. polymers separate based helium was used to continuously purge the mobile
on their hydrodynamic volume. Fischer and phase. To correct for any slight variation in the
coworkers [8,9] have used this technique to deter- pump speed, glycerol was added to the silica
mine the size distribution of nanometer-sized gold dispersion to serve as an internal timing marker.
particles and colloidal cadmium sulfide particles. The average experimental time to acquire data
G o o d separations between different sized particles from a single injection was about 55 rain.
were achieved. By examining the GPC fractions Calibration curves were generated with six
under an electron microscope, size distribution of narrow molecular weight pullulan standards. Ono
the particles were calculated. [11] gives details on the data analysis.
Chen et al. [10] have modified the GPC tech-
nique [ 1 l] to allow a quantitative determination 2.4. 3. Electrokinetic analysis." zeta potential
of the size distribution of nanometer-sized silica measurements [ 1 2 , 1 3 ]
particles. It was shown that water soluble pullulans Electrokinetic analysis was performed to
are suitably sized references to calibrate the GPC determine the charge characteristics of the silica
system, i.e. to convert retention volumes to particle dispersion. A Matec ESA System 8000 was used
dimensions. We characterized the size distribution to determine the zeta potential of the silica disper-
of our silica dispersions by this technique. sions. The electroacoustic effect is observed when
All GPC experiments were done with a 10 mM 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), the dynamic mobility. Here a is the particle radius,
c/m s-1 is the speed of sound in the continuous e the permittivity of the liquid, ~/ the dynamic
phase, Ap/g cm-3 is the density difference between viscosity, v the kinematic viscosity, and f the field
the particle and the continuous phase, factor. For very small values of a, i.e. a < 100 nm,
#(oJ)/gm cm s-1 V -1) the dynamic mobility at fre- G~ 1, and hence the inertial forces are unimport-
quency ~o/rad s- 1 and ~b the volume fraction. Gf is ant. In such cases, it is possible to determine the
the geometrical and acoustic gain factor. In prac- zeta potential directly from the mobility measured
tice it is convenient to lump ~ and Gf together and at a single frequency. For all the experiments
determine this ratio as one instrumental constant. described in this paper #(e~)= #(0). The field factor
At higher volume fractions (greater than 0.05) f = 1 was used and the synthesizer frequency was
7/Gf is dependent on the electrode/probe geometry set at 1 MHz. 1.25 wt.% silica dispersions were
and on the volume fraction. used to perform all the experiments.
The electroacoustic mobility or dynamic mobil-
ity #@o) is related to electrophoretic mobility #(0)
as described by O'Brien and coworkers, and is 3. Results and discussion
given by
The concentrations of TEOS, ammonia and
water, the reaction temperature and the mean
#(~o) =/~(0)G = ~-q (1 +f)G (7)
particle size measured by DLS are shown in
Table 1. These experiments were all performed
where G represents the effect of inertial forces on 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 was used to convert the retention volume values
times and the reported size is the average from the of the silica samples to corresponding viscometric
five runs. The deviations between the runs were radius values. The intrinsic viscosities and reten-
less than 5% for all the DLS experimental data tion volumes for the pullulan standards are given
reported here. in Table 2. The logarithms of intrinsic viscosity
When the TEOS concentration is increased for multiplied by molecular weight vs. retention
one particular concentration of ammonia and volume were plotted to obtain the calibration curve
water at a given temperature, particle size shown in Fig. 1. The curve which best fits the data
increases. This is consistent with the findings of was a third-order polynomial. The curves in Fig. 2
Bogush and Zukoski [3]. When the temperature is show the retention volume vs. normalized
increased for a given concentration of TEOS, concentration values for the silica samples. After
ammonia and water, the particle size decreases, as converting the retention volume values into the
observed by Tan et al. [5]. corresponding viscometric radius values, the nor-
The solid content of the resulting methanol malized concentration-viscometric radius plots for
dispersions varied from 1.25 to 1.5 wt.% for most all the silica samples are shown in Fig. 3. To
of the dispersions, except for R3 and R4 where compare the results from the dynamic light scatter-
the solid content was around 1 wt.%. The light ing experiments and the GPC experiments, z-
scattering experiments were performed on both average values were calculated. The expression for
dispersions in methanol and water and the same the z-average diameter is given by [14]
particle size was observed. Concentrated aqueous
2 (Wi/d31)
dispersions of silica were prepared by adding
dz - i (8)
appropriate quantities of water and then vacuum (w,/d:)
distilling to remove the methanol. The solid i
content of the final dispersions varied from 5 where wi is the weight fraction of particles with
to 7 wt.%. the viscometric diameter d. From Table 3, a reason-
GPC experiments were performed on the con- able agreement between the z-average diameter
centrated aqueous dispersions. A calibration curve value from GPC experiments with the diameter
value obtained from the DLS measurements can



L0 ~ ~ 8oe
, ', I:::H



112 ,13 |14 11.~ 16 17

Relentiocl V ~ u m ~ (ml)
...., "~', ,,, ,'~ ,~ ,', ,', ,, -

R~ention Volume(ml)
Fig. 1. Calibration curve for the GPC experiments. Vh is the
product of molecular weight and intrinsic viscosity. The curve Fig. 2. Normalized concentration vs. retention volume curves
is a third-order least squares polynomial fit to the data points. 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


,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

References [7]P. Stepanek, in: W. Brown (Ed.), Dynamic Light

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