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The synthesis of submicron silica particles by the hydrolysis and condensation of dilute and concentrated solutions of
tetraethyiorthosilicate (TEOS) has been studied in low molecular weight alcohols (C1-C4). A base (ammonia) was used to
catalyze the reaction. Raman spectroscopy, gas chromatography and the molybdate method were used to establish the
hydrolysis and condensation kinetics. Dynamic and classical light-scattering techniques were employed to monitor particle
growth and particle number concentration kinetics, and particle size distribution. The effects of solvent and TEOS
concentration on the degree of monodispersity of the particles are discussed. Further, the chemical and particle growth data
were used to test theories of homogeneous nucleation and aggregative growth, which have been proposed as mechanisms that
govern the growth of submicron monodisperse silica particles by TEOS hydrolysis.
Initial TEOS concentrations were 0.05M for dilute a dilute solution of colloidal particles. Those mea-
solutions and 1.0M for concentrated solutions. surements were carried out in a Perkin-Elmer
The chemical analysis included gas chromatog- Model 200 spectrometer. The method of calculat-
raphy, the molybdate method for soluble silica ing particle number concentration from CLS
determination, and Raman spectroscopy. A Tracor methods is discussed by Hulst [4]. The dynamic-
550 Gas Chromatograph equipped with a flame- light scattering (DLS) spectrometer used here has
ionization unit was used to follow the production been described in previous publications [5,6].
of ethanol. The glass chromatographic column was
packed with 1% SP1000 on 80/100 Carbopac C
and was operated at 130 ° C. 3. Theory
The molybdate method was used to monitor
the total soluble silica (TS) (i.e., unreacted TEOS 3.1. Chemistry and reaction kinetics
plus monomeric and some dimeric silicic acid) in
the reaction medium. The method was adapted Understanding the mechanisms which control
from the procedure given by Makrides et al. [3]. the formation of monodisperse silica by the base-
Raman spectroscopy was performed during the catalyzed hydolysis of TEOS requires an initial
hydrolysis of concentrated TEOS solutions in investigation of the chemical behavior of the hy-
ethanol. Before running Raman spectroscopic drolysis and condensation reactions. The overall
analysis, acetic anhydride was added to a sample hydrolysis and condensation reactions are given as
of the reaction medium. The acetic anhydride follows:
reduced the rate of hydrolysis by neutralizing the
[ O H - ] ions and flocculated the submicron par- Si(OC2H5)4 + 4 H 2 0 OH- )Si(OH)4 + 4C2HsOH,
ticles for easy filtration through a 0.22 ~m Duro- (1)
pore filter. Raman spectra were obtained in a
OH-
standard quartz spectrophotometer cell with the Si(OH)4 ~ SiO 2 $ + 2H20. (2)
use of a Spex 1404 spectrometer that was con-
Schmidt et al. [7] and Byers et al. [6] have pro-
trolled by a Compudrive microprocessor. The
posed a mechanism for the base-catalyzed hydrol-
sample was excited with the 488 nm line of a
ysis of TEOS where TEOS reacts with hydroxide
Spectra-Physics 165-06 argon ion laser and a power
ions and water to form a transition state complex
setting of 400 mW. The scattered light was col-
which decomposes to form monosubstituted silane,
lected at 90 o without a polarizer analyzer and was
alcohol, and hydroxide ions. Initially, the O H -
detected by a photomultiplier/photon counter
attacks the TEOS molecule by a nucleophilic reac-
(EMI No. 9863B350) device. The photomulti-
tion mechanism. Since nucleophilic attack is sensi-
p l i e r / p h o t o n counter was connected to an IBM
tive to the steric effects of the substitutes and the
PC-AT computer which housed a multichannel
electron density around the silicon atom, the fewer
analyzer board for data acquisition and display.
bulky and highly basic alkoxy groups surrounding
The characteristic peak at 790 cm-1 was used to
the silicon atom, the more rapid the attack by the
follow the TEOS concentration.
O H - . Thus, the controlling step will involve the
Classical and dynamic light scattering measure-
removal of the first alkoxy group and the mono-
ments were used to determine the intensity aver-
meric partially hydrolyzed products will hydrolyze
age particle size, the weight-averaged particle size
at a faster rate, tending to produce monomeric
distribution, and the particle number concentra-
silicic acid [8,9]. Using the above mechanism and
tion. All samples were diluted such that the par-
assuming that condensation occurs between com-
ticles were at least 20 diameters apart, thus mini-
pletely hydrolyzed species, the resulting rate ex-
mizing multiple scattering and particle-particle
pression for the hydrolysis reaction is
interactions. Classical-light scattering (CLS) mea-
surements were obtained by measuring the trans- d[TEOS]
dt k~ [H20] I o n - ] [TEOS ] . (3)
mittance of a 400 nm light source passing through
M.T. Harris et al. / Dilute and concentrated TEOS solutions 399
When ammonia is used as the base and the ioniza- 3.2. Controlled homogeneous nucleation and
tion reaction of ammonia with water is consid- aggregative growth
ered, eq. (3) becomes
d[TEOS] The theory of controlled homogeneous nuclea-
dt k~ [H20]"5[NH3 ]°'5[TEOS]. (4) tion involves slowly increasing the concentration
of a precipitable material, [Si(OH)4 ] and other
Iler [10] has proposed a mechanism for the con- silica species, to attain a degree of supersaturation
densation of silicic acid which also involves a at which nucleation becomes appreciable. Since
nucleophilic attack on the silicon by the hydroxide the generation of precipitable material is slow, the
ion. Thus, the rate of condensation should be formation of nuclei accompanied by the relief of
proportional to the concentration of base catalyst. supersaturation is restricted to a relatively short
In contrast, eq. (2) suggests that the dissolution period, and few new nuclei are formed after this
reaction should be proportional to [H20] 2. There- initial outburst. Subsequently, the nuclei grow by
fore, the rate equation for the silicic acid (eq. (2); the addition of monomer to its surface [11]. In this
[OH-] = constant) is mechanism, the final number of particles is essen-
d[Si(On)4] tially the same as the number of particles that are
at = k~ [H20]"5[NH3]°5[TEOS] produced during the short nucleation period.
Aggregative growth [2], which is based on the
- kc[Si(OH)4 ] + kDSp[H20] 2,
electric double layer theory, assumes that very
(5) small ( - 1-5 nm) nuclei, because of their colloidal
where Sp is the total surface area of the silica instability, rapidly coagulate to form larger, more
particles. This equation is expected to be applica- stable spherical particles. As nucleation proceeds,
ble if the condensation of silicic acid primarily the very small nuclei preferentially attach to the
yields nuclei. However, if the silicic acid is pre- larger particles rather than aggregate with other
cipitating on the surface of the particle, if [OH-] primary nuclei. Thus, the formation of monodis-
is constant, and if the rate of reaction is surface- perse spherical particles is achieved by the con-
reaction controlled, it is expected that the k c trolled aggregation of these nuclei.
should be proportional to the total surface area of
the silica particles. Therefore, eq. (5) becomes
4. R e s u l t s a n d d i s c u s s i o n
d[Si(OH),]
at k~q [H20]"5[NH3 ]°5[TEOS]
4.1. Hydrolysis and condensation reactions
- k~Sp[Si(OH),] + kDSp[H20] 2,
The concentration of TEOS in the reaction
(6)
medium is computed from the experimentally de-
or, considering the fact that k D / k ~ = [Si(OH)4le termined ethanol concentrations. In dilute and
= K[SiO2] , concentrated solutions, these data exhibited pseu-
do-first order kinetics with respect to the TEOS
d[Si(On)4]
dt k~ [H20]l5[NH3 ]°5[TEOS] concentration for the hydrolysis reaction. Previous
studies [6,12] have shown that this pseudo-first
- k~Sp [Si(OH)4] order rate constant, kr~, varies with [H20] 1"5 and
. 2 • [NH3] °'9. Table 1 lists the values of k~, the 'ab-
+ kDSp[H20 ] [S,O2] , (7)
solute' rate constant, for the hydrolysis of TEOS
where k ~ = k ~ K and [Si(OH)4]e is the equi- in each of the solvents. These data show that the
librium concentration of silicic acid. Equations rate of hydrolysis in the solvents decreases at
5-7 can be written in terms of the experimentally 1-butanol > methanol > 1-propanol > ethanol-2-
determined [TS] by noting that [TS] = [TEOS] + propanol. The effect of solvent on the rate of
[Si(OH)4]. hydrolysis has been observed by other investiga-
400 M.T. Harris et a L / Dilute and concentrated TEOS solutions
I I I I I I I I I I a n d 6.0M H 2 0 in m e t h a n o l , e t h a n o l , 1 - p r o p a n o l ,
1.000 ~] METHANOL --
A 2-PROPANOL --. 2 - p r o p a n o l , a n d 1-butanol. S i m i l a r to the rate of
~7 1 -BUTANOL
0.800 ~k~ 0 1 -PROPANOL -- hydrolysis, the rate o f c o n d e n s a t i o n d e c r e a s e d as
~" 0 ETHANOL --
1-butanol > methanol > 1-propanol > ethanol >
0.600
v 2 - p r o p a n o l . This is expected, since b o t h the hy-
o.,,oo drolysis a n d c o n d e n s a t i o n r e a c t i o n s involve a sim-
ilar r e a c t i o n m e c h a n i s m , i.e., the n u c l e o p h i l i c at-
0.200
tack on the silicon b y the h y d r o x i d e ion.
I n a d d i t i o n to the h y d r o l y s i s rate c o n s t a n t s ,
0
0 2 4 6 8 10 103 table 1 c o n t a i n s the rate c o n s t a n t s (i.e., k c, k ~ ,
TIME (s) k D a n d k ~ ) for the c o n d e n s a t i o n a n d d i s s o l u t i o n
Fig. 1. Total soluble silica: TEOS hydrolysis in various al- r e a c t i o n s w h e n eqs. (5), (6), o r (7) a r e used. T h e
cohols (1.0M TEOS, 0.7M NH4OH, 6.0M H20 ). total surface area, Sp = 4 N ~ f f z, was d e t e r m i n e d
f r o m the i n t e n s i t y a v e r a g e d p a r t i c l e radius, ~, a n d
the p a r t i c l e n u m b e r c o n c e n t r a t i o n , N, m e a s u r e -
m e n t s that were o b t a i n e d f r o m light s c a t t e r i n g
t o t s [13,14]. T h e relative rates o f the h y d r o l y s i s measurements. The condensation and dissolution
r e a c t i o n in 1 - b u t a n o l , 1 - p r o p a n o l , e t h a n o l a n d rate constants, which r e q u i r e Sp, were o n l y c o m -
2 - p r o p a n o l h a v e b e e n e x p l a i n e d in terms o f h y d r o - p u t e d for e t h a n o l (dilute a n d c o n c e n t r a t e d solu-
gen b o n d i n g a n d steric effects [6]. T h e u n e x p e c t e d tions) a n d 1 - p r o p a n o l (dilute solutions) b e c a u s e of
faster rate of h y d r o l y s i s in m e t h a n o l requires fur- flocculation, which resulted in e r r o n e o u s p a r t i c l e
ther i n v e s t i g a t i o n to d e t e r m i n e if this p h e n o m e n o n size m e a s u r e m e n t s for the o t h e r solvent systems.
is d u e to alcoholysis o r a l t e r a t i o n s in the b a s i c i t y T h e d a t a clearly show a large difference b e t w e e n
( c a u s e d b y h y d r o g e n b o n d i n g [15]) of the r e a c t i o n the c o n d e n s a t i o n rate c o n s t a n t , k c (eq. (5)), for
medium. the 1 M a n d 0.05M T E O S solutions. O n the o t h e r
F i g u r e 1 shows the c o n d e n s a t i o n kinetics for h a n d , k ~ (eq. (6)) was a p p r o x i m a t e l y equal for
the h y d r y l o s i s of 1 M T E O S with 0.7M N H 4 O H the h y d r o l y s i s of the 1M a n d 0.05M T E O S solu-
Table 1
Summary of results for TEOS hydrolysis in various alcohols
Solvent [TEOS] k~I a) Eq. kC k~- k D b) k• c) r2
(mol/l) (rain - 1) (rain - 1cm)
methanol 1.0 0.0036
ethanol 0.05 5 0.0015 1.4×10 -8 0.998
ethanol 1.0 0.0025 5 0.0119 6.0 >(10-7 0.975
ethanol 0.05 6 0.00029 4.7×10 .8 0.995
ethanol 1.0 0.0025 6 0.00031 7.8×10 .7 0.980
ethanol 0.05 7 0.00021 8.0>(10 -7 0.997
ethanol 1.0 7 0.00023 8.8>(10 -7 0.992
1-propanol 0.05 0.0031 6 0.00039 4.2×10 -8 0.980
1-propanol 0.05 0.0031 7 0.00056 1.2>(10 .6 0.989
1-propanol 1.0 0.0030
2-propanol 0.05 0.0018
2-propanol 1.0 0.0019
1-butanol 0.05 0.0058
1-butanol 1.0 0.0057
a) min- 1 (mol/l)- 2.4.
b) min - 1 cm(mol/1)- 1.
c) rain- l cm(mol/1)- 2.
M.T. Harris et aL / Dilute and concentrated T E O S solutions 401
X I0 -2
6
I
4.2. Particle size, size distribution, and particle
number concentration
4
\ E1 EXPERIMENTAL [TS]
A THEORETICAL [SI(OH)4 ]
O EXPERIMENTAL [SI(OH)4 ]
THEORETICAL [TS]
Figure 3 shows the intensity-averaged particle
o
E 3
\ \ ElN o l I THEORETICAL [TEOS] size and particle number concentration for the
hydrolysis of 1M TEOS in ethanol with initial
[ H 2 0 ] = 6.0M and [NH4OH ] = 0.7M. The figure
•~ El\ shows that the initial particle radius starts at ap-
proximately 0.05 rtm and continues to grow to a
1
final particle radius of 0.135 t~m. Thermodynamic
consideration suggests that the initial particle size
0
I I l I ~ "~ "" l " "~'--- -L .iJ __ 1 I (i.e., nuclei) should have been 0.001 to 0.005 I~m.
0 40 80 120 160 200 240 It requires about 10 s to obtain particle size mea-
TIME (rain)
surements by dynamic light scattering. Therefore,
Fig. 2. TEOS hydrolysis in ethanol (0.05M TEOS, 0.7M as suggested by the aggregative growth mecha-
NH4OH, 6.0M H20 ).
nism, the very small nanometer size nuclei rapidly
aggregate to form the larger more stable colloids.
0.8
~,. ?/"% 0.05M TEOS sample. Transmission electron mi-
croscopy has shown that this occurs in all of the
,.~ O.E i '?' \ solvent systems except 1-butanol where the par-
ticle size was essentially the same but the size
~ 0.4 distribution broadened as the initial TEOS con-
centration increased. Further, the particle size dis-
No tribution in all the solvents is about the same;
thus, the solvent has little effect on the degree of
0,03
monodispersity for the reaction conditions of this
0.05 0.07 0.09 0.11 0.13 0.15 0.17 0.19 0.21
The authors express their gratitude to Mike [8] K.D. Keefer, Mater. Res. Soc. Symp. Proc. 32 (1984) 15.
Burgess for his careful efforts in performing the [9] S. Sakka, H. Kozukz and S. Kim, in: Ultrastructure
Processing of Advanced Ceramics, eds. J.D. Mackenzie,
experiments in this program.
and D.R. Ulrich (Wiley, New York, 1988) p. 159.
[10] R.K. Iler, The Chemistry of Silica (Wiley, New York,
1979).
References [11] V.K. LaMer and R.H. Dinegar, J. Am. Chem. Soc. 72
(1950) 4847.
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[2] G.H. Bogush and C.F. Zukoski IV, in: Ultrastructure thosilicate reactions in alkaline-alcohol solvents, pre-
Processing of Advanced Ceramics, eds. J.D. Mackenzie, sented at the AIChE Annual Meeting, New York (Nov.
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