Colloids and Surfaces

A: Physicochemical and Engineering Aspects 197 (2002) 7 – 17

www.elsevier.com/locate/colsurfa

Preparation of silica nanoparticles: determination of the

optimal synthesis conditions for small and uniform particles
Sung Kyoo Park, Ki Do Kim, Hee Taik Kim *
Department of Chemical Engineering, Hanyang Uni6ersity, 1271 Sa 1 -Dong, Ansan, Kyunggi-do 425 -791, South Korea

Received 12 October 2000; accepted 6 March 2001

Abstract

Silica nanoparticles were prepared from tetraethylortho-silicate (TEOS) dissolved in ethanol by using a semi-batch
process in order to control the particle properties. In this work, the statistical experimental method was also used to
compare the properties (particle size and SD) of the SiO2 particles according to the four parameters (R =[H2O]/
[TEOS]), concentration of ammonia (NH3), the feed rate of reactant, reaction temperature]. We have obtained
monodispersed silica particles having size ranging from 10 to 350 nm by our experiment. It was found that the
optimal synthesis conditions for the preparation of SiO2 nanoparticles with narrow size distribution in semi-batch
process were as follows; (R =[H2O]/[TEOS], 30 – 55; concentration of ammonia (NH3), 0.2– 0.35 mole l − 1; feed rate
of reactant, 13–17 cm3 min − 1; reaction temperature, 55 – 65°C). The above-mentioned optimal conditions were used
to prepare the particles with minimum particle size (30 nm) and its SD ( B 9 5 nm), simultaneously. Experimental
results measured by using the optimal synthesis conditions were in a good agreement with simulated value and the
smallest size ( 10 nm in diameter) was obtained. Also, we found that the effect of parameters on the particle size
and SD in the preparation of SiO2 nanoparticles was increased in the following order; reaction temperature,
(R =[H2O]/[TEOS]); concentration of ammonia (NH3), feed rate of reactant. © 2002 Elsevier Science B.V. All rights
reserved.

Keywords: Silica; Nanoparticle; Semi-batch; Statistical experimental method

1. Introduction pharmacy, etc. [1]. Of these particles, SiO2

The importance and advantages of mono-
dispersed nanometer-sized particles were shown
not only in the scientific field, but also in various
industrial applications, e.g. catalysts, pigments,
* Corresponding author. Tel.: + 82-31-4005274; fax: +82-
31-4197203.
E-mail address: khtaik@email.hanyang.ac.kr (H.T. Kim).
nanoparticles are used to make electronic sub-
strates, thin film substrates, electrical insulators,
thermal insulators, humidity sensors, etc. The sil-
ica particles play a different role in each of these
products. The quality of some of these products is
highly dependent on the size and size distribution
of the silica particles. Commercial silica has a
broad size distribution and varying levels of metal
contaminants. It is imperative to have silica parti-

0927-7757/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 1 ) 0 0 6 8 3 - 5
8 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17

cles of narrow size distribution and high purity to Table 1

Orthogonal array L8 (27)
conduct model studies [2]. Thus, we prepared SiO2
nanoparticles by sol-gel method using a semi-batch Trial number Factors
process that is easier than batch process for con-
trolling the size and its distribution. A B C D E F G
Bogush and Zukoski [3] prepared mono-
1 1 1 1 1 1 1 1
dispersed silica particles having sizes ranging from
2 1 1 1 2 2 2 2
40 nm to several micrometers by controlled hydrol- 3 1 2 2 1 1 2 2
ysis of tetraethylortho-silicate (TEOS) in ethanol, 4 1 2 2 2 2 1 1
followed by condensation (polymerization) of the 5 2 1 2 1 2 1 2
dispersed phase material. The reactions are written 6 2 1 2 2 1 2 1
7 2 2 1 1 2 2 1
in abbreviated form as
8 2 2 1 2 1 1 2
Si(OR)4 +4H2O “Si(OH)4 +4ROH
(hydrolysis) ethanol solution with ammonium hydroxide (NH3
Si(OH)4 “SiO2 +4H2O (condensation) 28%, Yakuri Pure Chemicals Co.). Ammonia was
used as a catalyst. The reactants were used as
They found that five primary parameters affect prepared without any purification. The solutions
on the size and size distribution of silica particles. were prepared in a glove box at room temperature
They were, (1) concentration of TEOS; (2) concen- under dry air. The humidity in the glove box was
tration of ammonia; (3) concentration of water; (4) kept below a few percent.
alcohol used as the solvent; (5) reaction tempera-
ture. 2.2. Synthesis of silica nanoparticles
In this paper, we examine the effects of R
(=[H2O]/[TEOS]), concentration of ammonia Monodispersed spherical silica nanoparticles
(NH3), feed rate of reactant, and reaction temper- were prepared by the hydrolysis of TEOS in a
ature on the formation of SiO2 nanoparticles. In semi-batch reactor. A schematic design of a semi-
addition, to establish the optimal synthesis condi- batch process is depicted in Fig. 1. The apparatus
tions and to find the main parameters affecting the consists of a reservoir of starting solutions, a
properties of SiO2 nanoparticles, we used a statis- micro feed pump to supply the solutions, a water
tical experimental optimization program (Pro-Opt. bath, and a reactor with stirrer. A micro feed
Ver. 1.02) based on Taguchi method [4–6]. The pump with a constant flow rate fed the starting
purpose of the statistical experimental method [7] solution A (TEOS and ethanol) into the reactor
is to help us obtain the highest cost-worth for our that contains another solution B (water, ethanol
materials and products and find the main parame-
ters affecting the properties (Table 1). We also
report a good agreement between the simulated
particle size obtained by the statistical experimental
program and the experimental results.

2. Experimental method and data treatment

2.1. Starting solutions

In this present work, the starting solutions were Fig. 1. Schematic diagram of experimental apparatus. (1) water
TEOS (99.9%, Aldrich Chemical Co.), ethanol bath, (2) microfeed pump, (3) stirrer, (4) reactor, (5) N2 gas, (6)
(99.9%, Sigma Chemical Co.) solution, and water- Et(OH)/water/NH3 solution, (7) Et(OH)/TEDS solution.
 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17 9

Table 2 2.4. Characterization of silica nanoparticles

Experimental parameters and desirable properties

Parameter Property
[H2O]/[TEOS], 25–155 Size (nm), minimize
Feed rate (cm3 min−1), 0.6–18.0
NH3 (mole l−1), 0.2–1.0 STD (nm), minimize
Temperature (°C), 15–70
and ammonia) and the experiment was conducted
with dry nitrogen.
2.3. Design of statistical experiment
The operational parameters and desirable prop-
erties for the synthesis are summarized in Table 2.
As shown in Table 2, it is necessary to control the
four parameters affecting the properties (particle
size and particle size distribution) for the prepara-
tion of nanoparticles. Therefore, we used a statis-
tical experimental program (Pro-Opt. Version
1.02) to find the optimal conditions for satisfying
the two properties at the same time. A design of
the orthogonal arrays by a statistical experimental
program and its experimental results obtained by
a laser particle size analyzer are shown in Table 3.
We carried out twelve experiments and took three
levels for each factor.
Particle size, particle size distribution, and
shape of the powders were determined by a Field
Emission Scanning Electron Microscopy (FE-
SEM, JEOL, JSM-6330F, Japan), Transmission
Electron Microscopy (TEM, JEOL, JEM-2010,
Japan), and a Laser Particle Size Analyzer (Ot-
suka electronics, LPA-3000, 3100, Japan).
3. Results and discussion
3.1. Determination of the optimal conditions to
find the desirable properties
We obtained the correlation coefficients of each
parameter from the results of Table 4 that affect
particle size and its distribution by a statistical
experimental optimization method. In addition,
the values of confidence level (R 2) were calculated
from regression analysis. These results are shown
in Table 4. Table 4 indicates that the correlation
function of particle size (R 2 = 0.99) is more reli-
able than that of particle size distribution. From
the data of each property in Table 3, the graphs
of two properties about each parameter were
obtained.

Table 3
Orthogonal arrays for statistical experiment and results

Experiment Preparation conditions Results

number
H2O/TEOS Feed rate NH3 Temperature Average particle size SD
(cm3 min−1) (moles l−1) (°C) (nm) ( 9 nm)

1 25 0.6 0.2 15 70.4 26.5

2 25 18 1.0 15 64.8 11.3
3 25 0.6 1.0 70 38.6 6.5
4 25 18 0.2 70 10.2 6.1
5 155 0.6 1.0 15 236.4 76.1
6 155 18 0.2 15 129.6 7.7
7 155 0.6 0.2 70 21.6 6.3
8 155 18 1.0 70 136.7 80.4
9 90 9.3 0.6 42.5 123.0 2.5
10 90 9.3 0.6 42.5 121.5 3.2
11 90 9.3 0.6 42.5 124.9 3.8
12 90 9.3 0.6 42.5 120.1 2.1
10 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17

Table 4
Correlation coefficient of each parameter and confidence level of propertiesa

Coefficients R2

Constant R NH3 Feed rate Tempearture R×NH3 R×feed rate NH3×feed

rate

Size (nm) 10.471 −0.166 400.35 0.873 −0.683 −0.144 0.044 −20.517 0.99
STD (nm) 9.225 0.037 19.522 1.512 −0.345 0.384 −0.011 −2.729 0.91

a
R= [H2O]/[TEOS]; R 2, confidence level.

Figs. 2, 3 and 5 are the simulated results ob- tained from the optimal conditions of Table 5 by
tained by a statistical experimental optimization using optimization program were compared with
program from the results of Table 4. Fig. 2 shows the experimental values (Table 6). Table 6 shows
the simulated results of the relation of particle size
and four parameters. Fig. 2(a) illustrates that the
particle size decrease while increasing the feed rate
of reactant and reaction temperature. It was also
found that, however, the increase in the R (=
[H2O]/[TEOS]) and ammonia concentration re-
sults in large particle size (Fig. 2(b)). Fig. 3
represents the effect of parameters on particle size
distribution. SD of SiO2 particles decreases with
reducing of the feed rate and rising of reaction
temperature (Fig. 3(a)). Fig. 3(b) shows that the
SD of SiO2 particles increases at a high concentra-
tion of water and ammonia. Fig. 4 is the SEM
images of SiO2 particles prepared by a design of
the statistical experiment (Table 3).
So far, we discussed the effect of parameters
((R = [H2O]/[TEOS]), concentration of ammonia,
feed rate of reactant, and reaction temperature)
on properties (particle size and size distribution)
to find the optimal conditions for each parameter.
However, it is necessary to find the overall opti-
mal synthesis conditions that can synthesize nano-
sized particles having a narrow size distribution.
If only one of two properties is satisfied,
monodispersed nanoparticles are not prepared. In
this work, therefore, the optimal conditions for
satisfying the minimum particle size (B 30 nm)
and SD ( B 95 nm) simultaneously should be
found. These results are shown in Fig. 5. In Fig.
5, the vertical axis is a normalization, which indi-
cates probability to satisfy desired property as it is
approaching to 1.0. In addition, the overall opti-
mal conditions to satisfy the desirable properties Fig. 2. Simulated results of parameters effect on particle size
are represented in Table 5. Simulated values ob- (nm).
 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17
Fig. 3. Simulated results of parameters effect on SD of particle
size (nm).
that experimental values of properties obtained
by a laser particle size analyzer were in a good
agreement with simulated value. Particle size
(R 2 =0.99) was in better agreement with the sim-
ulated value than particle size distribution. These
agreements between two values can also be pre-
dicted from the confidence level (R 2) as shown in
Table 4. Figs. 6 and 7 are, respectively, TEM
image and particle size distribution of SiO2
nanoparticles determined by a laser particle size
analyzer, which was prepared under the condi-
tions of Table 5. The synthesis conditions are; R
(= [H2O/TEOS]), 30.6; concentration of ammo-
nia (mole l − 1), 0.32; feed rate of reactant (cm3
min − 1), 17; reaction temperature (°C), 62.
11
3.2. Effect of the concentration of water and
ammonia
There was an increase in mean particle diame-
ter with increasing water concentration and am-
monia concentration (Fig. 2(b)). To minimize the
particle size, the value of R (= [H2O]/[TEOS])
and ammonia concentration must be decreased.
Hydrolysis is a very slow reaction, even if an
acid or a base is used as a catalyst. Ammonia
usually acts as a catalyst for the hydrolysis and
condensation of TEOS. It is apparent that the
higher ammonia and water concentration must
attribute to the higher hydrolysis rate.
Matsoukas and Gulari [8] reported that the
effect of ammonia concentration is to promote
hydrolysis, but also to promote the polymeriza-
tion (condensation) rate, resulting in faster kinet-
ics, and lager particle sizes. In many other
studies, the same result was observed.
However, they reported that the increase in
water concentration leads to smaller particles.
On the contrary, the large particle size was ob-
tained in the higher water concentration by our
experiments. We can explain this as follow. If
high water concentration is applied, a high nucle-
ation rate occurred, so a lot of small sub-parti-
cles are prepared at a short period. But, the
hydrogen bond of SiO2 sub-particles under the
condition of a higher water concentration is
stronger than that of a lower water concentra-
tion because of excess water. Therefore, sub-par-
ticles in the higher water concentration
agglomerate each other and grow into a large
particle. Fig. 8 shows SEM image of SiO2 parti-
cles obtained in the higher water concentration
and the lower ammonia concentration. The mor-
phology indicates that small sub-particles have
grown into a large particle by agglomeration.
Fig. 9 illustrates the effect of the water concen-
tration on the particle size and its distribution.
The effect of concentration of water and ammo-
nia on the particle size distribution is alternative
as shown in Fig. 3(b). But, it is sure that high
concentration of water and ammonia attributes
to broaden the particle size distribution.
12 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17

Fig. 4. SEM images of SiO2 particles prepared by a design of the statistical experiment. (a) Exp. No. 1, (b) Exp. No. 3, (c) Exp. No.
5, (d) Exp. No. 8, (e) Exp. No. 9, (f) Exp. No. 11.
 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17
Fig. 5. Simulated results of parameters effect on overall prop-
erties.
3.3. Effect of feed rate of reactant
To explain effect of feed rate, we compared a
semi-batch system with a batch system. Although
we used a semi-batch system in our experiment, it
can be considered as a batch system at a rapid
feed rate of reactant, because it just takes a few
minutes to finish feeding of reactant and hydroly-
sis is a very slow reaction.
LaMer and Dinegar [9] proposed the self-nucle-
ation model of monodispersed particle produc-
tion. There are three regimes in the generation of
13
Table 5
Optimal synthesis conditions
Parameter Range
R [H2O/TEOS] 30–55
NH3 (mole l−1) 0.2–0.35
Feed rate (cm3 min−1) 13–17
Temperature (°C) 55–65
monodispersed particles for use as ceramic pow-
ders. The first period is induction time, during
which the reaction slowly generates growth units
of the solid. The concentration in solution builds
up until a critical supersaturation (C*min) is
reached, when nucleation occurs. A relatively
short nucleation period produces a narrow size
distribution of nuclei and relieves the supersatura-
tion to below the critical values, preventing fur-
ther nucleation. After nucleation, growth
proceeds until the reaction stops due to equi-
librium solubility (Cs).
There should be a difference between a semi-
batch system and a batch system, considering a
LaMer and Dinegar’s model. Using a batch sys-
tem, accumulation rate of growth units to a criti-
cal supersaturation concentration (C*min) is faster
than that of a semi-batch system because reactant
solution A (TEOS and ethanol) and B (water,
ethanol and ammonia) is fed into the reactor
instantaneously. Thus, induction time of a batch
system is shorter than that of a semi-batch system.
And after slightly longer nucleation occurred, the
solute concentration is decreased to reach to the
equilibrium solubility (Cs). On the contrary, using
a semi-batch system, reactant A (TEOS and etha-
nol) is fed into the reactor that contains reactant
Table 6
Comparison of the properties between simulated and experi-
mental valuea
Simulated value Experimental value
Size (nm) 13.3 13.7
STD (nm) 93.2 94.5
a
Synthesis condition, R [H2O/TEOS]= 30.6; NH3 (mole
l ) =0.32; feed rate (cm3 min−1) =17; temperature (°C)=
−1
62.
14 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17

Fig. 6. TEM image of dispersed SiO2 nanoparticles prepared

by optimal experimental conditions of Table 5. Fig. 8. SEM image of SiO2 particles obtained in high water
concentration.

solution B (water, ethanol and ammonia) by a
micro feed pump. Therefore, accumulation rate of
growth units to a critical supersaturation concen-
tration (C*min) is slower than that of a batch
process. And the shorter nucleation occurred be-
cause reactant solution A is not supplied suffi-
ciently to keep the solute concentration above the
critical supersaturation concentration (C*min). Fi-
nally, the longer growth takes place in semi-batch
system. Fig. 10 shows a difference between a
semi-batch system and a batch system in the
generation of SiO2 particles. Consequently, the
SiO2 particles prepared by batch process are
smaller than the particles obtained by the semi-
batch process because the growth time of SiO2
particles in the semi-batch system is longer than
that of the batch system as shown in Fig. 10.
Therefore, using a semi-batch system, the
higher feed rate is applied, the smaller SiO2 parti-
cles are produced. In addition, by using the semi-

Fig. 7. Particle size distribution of SiO2 nanoparticles prepared by optimal experimental conditions of Table 5.
 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17 15

Fig. 9. Effect of water concentration on particle size and size distribution.

batch system, it is possible to prepare the parti- 4. Conclusions

cles having a narrow size distribution at a low
feed rate of reactant because of a relatively
short nucleation period.
3.4. Effect of the reaction temperature
Fig. 2(a) shows that the increase of reaction
temperature results in the decrease of particles
size. Following equation explains the effect of
the reaction temperature on homogeneous nucle-
ation from liquid phase [10].
SiO2 nanoparticles were prepared from the hy-
drolysis and condensation of TEOS by using a
semi-batch process. Ammonia was used as a cat-
alyst. The properties of SiO2 nanoparticles were
controlled by varying the molar ratio R (=
[H2O/TEOS]), concentration of ammonia (NH3),
feed rate of reactant solution (TEOS/Et(OH))
and reaction temperature. Statistical experimen-
tal method was used to find the condition to
minimize the particle size and its distribution.

J=J0 exp
 − DGDn 
exp
−DG* n (1)
kT kT

where, J stands for nucleation rate (1 l s − 1); J0

is initial nucleation rate (1 l s − 1); DGD denotes
diffusion activation free energy change (J); DG*
represents critical nucleation free energy change
(J); k denotes Boltzman constant (J K − 1); and
T is reaction temperature (K).
In Eq. (1), if reaction temperature (T) goes
up, the value of nucleation rate (J) must be
increased. Consequently, the mean particle size
relatively decreased due to the high nucleation
rate. And small particle size having narrow size
distributions can be obtained at high reaction Fig. 10. Effect of feed rate on particle size and size distribu-
temperature. tion. (a) batch system, (b) semi-batch system.
16 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17
As a result of this work, the main factors
affecting the preparation of SiO2 nanoparticles
were in the following order; reaction temperature,
R (=[H2O]/[TEOS]), concentration of ammonia
(NH3), feed rate of reactant. In addition, the
optimal synthesis conditions obtained by the ex-
perimental design method were as follows, R (=
[H2O/TEOS]), 30– 55; concentration of ammonia
(NH3) (mole l − 1), 0.2 – 0.35; feed rate of reactant
(cm3 min − 1), 13 – 17; reaction temperature (°C),
55 –65. The above-mentioned optimal conditions
were used to prepare the particles with minimum
particle size (B30 nm) and its SD (B 9 5 nm),
simultaneously. Therefore, the experimental val-
ues of particle size and SD were 13.7, 94.5 (nm).
By using the above optimal synthesis conditions,
mean diameters as small as 13 nm were obtained
and the properties of experimental results were in
a good agreement with the simulated data.
Appendix A. Statistical experimental method
Taguchi constructed a special set of orthogonal
arrays (OAs) to lay out his experiments. The use
of Latin squares orthogonal arrays for experiment
designs dates back to the time of World War II.
By combining the orthogonal Latin squares in a
unique manner, Taguchi prepared a new set of
standard OAs to be used for a number of experi-
mental situations. A common OA for 2-level fac-
tors is shown in Table 1.
This array, designated by the symbol L8, is used
to design experiments involving up to seven 2-
level factors. The array has eight rows and seven
columns. Each row represents a trial condition
with factor levels indicated by the numbers in the
row. The vertical columns correspond to the fac-
tors specified in the study. The OA facilitates the
experiment design process. To design an experi-
ment is to select the most suitable orthogonal
array, assign the factors to the appropriate
columns, and finally, describe the combination of
the individual experiments called the trial condi-
tions. Let us assume that there are at most seven
2-level factors in the study. Call these factors A,
B, C, D, E, F and G, and assign them to columns
1, 2, 3, 4, 5, 6, and 7, respectively of L8. The table
identifies the eight trials needed to complete the
experiment and the level of each factor for each
trial run. The experiment descriptions are deter-
mined by reading numerals 1 and 2 appearing in
the rows of the trial runs. A factorial experiment
would require 27 or 128 runs, but would not
provide appreciably more information.
In most cases, the Taguchi experiment design
requires the least number of test runs. A full
factorial experiment with 15 factors at 2 levels
each requires a test matrix with 32 768 (215) test
runs. A fractional factorial experiment with an
orthogonal array suitable for fifteen 2-level fac-
tors consists of 16 test runs.
In the Taguchi method the results of the exper-
iments are analyzed to achieve one or more of the
following three objectives, (1) To establish the
best or the optimum condition for a product or a
process; (2) to estimate the contribution of indi-
vidual factors; (3) to estimate the response under
the optimum conditions. The optimum condition
is identified by studying the main effects of each
of the factors. The main effects indicate the gen-
eral trend of the influence of the factors. Knowing
the characteristic, the levels of the factors, which
are expected to produce the best results, can be
predicted. The analysis of variance (ANOVA) is
the statistical treatment most commonly applied
to the results of the experiment to determine the
percent contribution of each factor. Study of the
ANOVA table for a given analysis helps to deter-
mine which of the factors need control and which
do not.
Taguchi suggests two different routes to carry
out the complete analysis. First, the standard
approach, where the result of a single run, or the
average of repetitive runs, is processed through
main effect and ANOVA analyses as identified
above. The second approach, which he strongly
recommends for multiple runs, is to use signal to
noise ratio (S/N) for the same steps in the analy-
sis. S/N analysis determines the most robust set of
operating conditions from variations within the
results.
S
= − 10 log10(MSD) (A1)
N
 S.K. Park et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 197 (2002) 7–17 17

where MSD is mean squared deviation from the weight, surface finish, etc.; m= target value of
target value of the quality characteristic. Consis- results (above); n= number of repetitions (yi ).
tent with its application in engineering and sci-
ence, the value of S/N is intended to be large;
hence the value of MSD should be small. Thus
References
MSD is defined differently for each of the three
quality characteristics considered, smaller, nomi- [1] G. Herbert, J. Eur. Ceram. Soc. 14 (1994) 205.
nal or larger. [2] S. Sridhar, D.H. Rasmussen, F.P. Chen, R.K. Kannabi-
For smaller is better ran, Colloids Surf. A Physicochem. Eng. Aspects 132
(1998) 45.
y 21 +y 22 +y 23 +··· [3] G.H. Bogush, C.F. Zukoski, J. Non-Cryst. Solids 104
MSD = (A2)
n (1988) 95.
[4] R. Roy, A Primer on the Taguchi-Method, Van Nostrand
For nominal is the best Reinhold, NewYork, 1990.
[5] T. Bendell, Taguchi Methods, Elsevier, New York, 1988.
(y1 −m)2 +(y2 −m)2 +··· [6] W.A. Talyor, Optimization and Variation Reduction in
MSD = (A3)
n Quality, McGraw-Hill, Singapore, 1991.
[7] K.D. Kim, H.T. Kim, J. Ind. Eng. Chem. 6 (2000) 212.
For bigger is better [8] T. Matsoukas, E. Gulari, J. Colloid Interf. Sci. 124 (1988)
1/y 21 +1/y 22 +1/y 23 +··· 252.
MSD = (A4) [9] V.K. Lamer, R.H. Dinegar, J. Am. Chem. Soc. 72 (1950)
n 4847.
where y1, y2, etc.= results of experiments, obser- [10] A.C. Pierre, Introduction to Sol-Gel Processing, Kluwer
vations or quality characteristics such as length, Academic Publishers, Boston, 1988.