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X-ray diraction of silica gels made by solgel method under

dierent conditions
Kanichi Kamiya
*
, Tomonori Dohkai, Masanori Wada, Tadanori Hashimoto,
Jun Matsuoka, Hiroyuki Nasu
Department of Chemistry for Materials, Faculty of Engineering, Mie University, Mie 514, Kamihama, Tsu Mie, Japan
Received 29 October 1997; received in revised form 2 February 1998
Abstract
Silica gels made from tetraethylorthosilicate (TEOS) under the basic condition and one made by two-step hy-
drolysis were studied by X-ray radial distribution function and correlation function analyses, and
29
Si NMR. X-ray
scattering intensity, the medium range feature of the radial distribution function (RDF) curve and correlation function
curve of silica gels was dierent from those of melt-derived silica. No dierence in X-ray data was noted among the gels.
The X-ray RDF data of the silica gels prepared under the basic condition and by the two-step by hydrolysis method
were explained by using a medium-range-order (MRO) structure model consisting of fourfold siloxane ring units in-
stead of sixfold siloxane rings which prevail in the melt-derived silica glass. It was estimated that the primary particles of
the acid-catalyzed silica gels built up by fourfold rings were around 1.0 nm in size, and those of the base-catalyzed silica
gels were a little larger. 4050% of silicon atoms in the primary particle in the acid-catalyzed gels, and 6070% of silicon
in the base-catalyzed gels were bonded to other particles through forming SiOSi bonds. The remaining silicon atoms
were terminated by forming SiOH bonds which were considered to stabilize the fourfold siloxane ring unit in the
gels. 1998 Elsevier Science B.V. All rights reserved.
1. Introduction
Solgel process for making silica glass consists
of hydrolysis of alkoxides to form silicon ox-
yalkoxy oligomers which are then condensed to
form silica gels. The porous silica gel is converted
to silica glass by heat treatment.
Much eort has been paid to approach the
chemistry involved in the alkoxide-to-sol trans-
formation by using techniques such as infrared
(IR) and/or Raman spectrosopy, chromatography,
29
Si NMR and viscosity analyses. Data obtained
have been reviewed by Brinker and Scherer [1], and
Sakka [2]. In the early stage of hydrolysis and
condensation reactions of the silicon alkoxide
tetraethylorthosilicate (TEOS) or tetramethyl
orthosilicate (TMOS) silicon oxyalkoxy oligomers
consisting of cyclic tetramers (or fourfold siloxane
rings) are predominantly formed [3,4]. Silica glass
obtained by heat-treating the alkoxy-derived silica
gel is known to possess the chemical and physical
properties near that of melt-derived silica glass. An
alkoxy-derived silica glass has been demonstrated
to have the same structure as the melt-derived glass
by several vibrational spetroscopy and diraction
studies, which implies that the ring structure units
composed of six SiO
4
tetrehedra or sixfold siloxane
rings are present in alkoxy-derived silica glass.
Journal of Non-Crystalline Solids 240 (1998) 202211
*
Corresponding author. Tel.: +81-592 319 436; fax: +81-592
319 471.
0022-3093/98/$ see front matter 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 9 8 ) 0 0 7 0 1 - 7
A number of studies devoted to structure
analysis of silica wet gels or xerogels [1,2] include
vibrational spetroscopy and
29
Si NMR measure-
ments which provided structure information about
the local surroundings of silicon atoms in the silica
gels. It has been found that the local chemical en-
vironment of silicon atoms or the short range order
(rst coordination sphere of silicon) in the gel
gradually develops in the silica glass as the sol-to-
gel transformation progresses. The amount of Q
4
species of silicon or SiO
4
structure units gradually
increases depending on hydrolysis parameters such
as the amount of water, catalyst and concentration
of the starting alkoxide. It is dicult to ascertain
the medium-range-order (MRO) of the gels or the
mode of linkage of SiO
4
tetrahedra by vibrational
and NMR spectroscopies. And, the query whether
the fourfold siloxane rings in the siloxane oligo-
mers formed in the early stage of the hydrolysis of
the silicon alkoxide is retained in the resultant gel
remains to be claried. In order to access the MRO
of the amorphous materials, the X-ray, neutron or
electron diraction method would be superior to
the vibrational methods. Several diraction studies
have been conducted on alkoxy-derived silica
xerogels. Esquivias et al. [5] used X-ray radial dis-
tribution to estimate skeletal density of silica gel,
but they did not mention MRO. Himmel et al. [6,7]
explained the shift of the rst sharp diraction peak
(FSDP) in the X-ray scattering intensity curve of
the silica gel in terms of the MRO composed of
eight puckered sixfold siloxane rings. The present
authors [8,9] made neutron and X-ray diraction
study of the silica gels derived from TEOS under
acidic condition, and elucidated the FSDP and
peaks in the RDF curve in the range from 0.3 to
0.7 nm (MRO) using the MRO model which con-
tains fourfold siloxane ring units. We reported that
this fourfold siloxane ring model simulates well the
RDF curve of silica gels with formulae CH
3
SiO
3=2
and HSiO
3=2
made from trifunctional silicon alk-
oxides CH
3
Si(OC
2
H
5
)
3
and HSi(OC
2
H
5
)
3
[10,11].
X-ray structure study based on the RDF and
correlation function analyses is here extended to
TEOS-silica gels made under basic conditions and
by the two-step hydrolysis method. Correlation
function analysis was applied to the acid-catalyzed
silica gels and MRO structure of silica gels, in-
cluding acid-catalyzed silica gels, is discussed.
2. Experimental
TEOS, Si(OC
2
H
5
)
4
, was used as a silica source.
Three silica gels, BR3, BR4 and AB gels were
prepared using conditions listed in Table 1. BR3
and BR4 were obtained by ammonia water-cata-
lyzed hydrolysis with R (molar ratio of water to
TEOS) of 3 and 4, respectively. AB gel was ob-
tained by the two-step hydrolysis reaction, in
which TEOS was rst partially hydrolyzed under
the acidic condition, followed by the addition of
excess amount of water under the basic condition
to complete hydrolysis. Other gels in Table 1, i.e.,
AR2, AR10 and HAR3 gels were used for com-
parative examination. AR2 and AR10 were pre-
pared by HCl-catalyzed hydrolysis with R of 2 and
10, respectively. The silica gel HAR3 was prepared
from triethoxysilane, HSi(OC
2
H
5
)
3
(HTES) with
R of 3 under the acidic condition. All gels were
Table 1
The composition of the starting alkoxide solutions and morphology of the resultant silica gels
Sample Composition (molar ratio) Gel morphology
Si(OC
2
H
5
)
4
C
2
H
5
OH H
2
O HCl NH
4
OH
AR 2 1.0 1.0 2.0 0.01 ) Fiber
AR 10 1.0 1.0 10.0 0.01 ) Bulk
BR 3 1.0 6.0 3.0 ) 0.01 Bulk
BR 4 1.0 3.0 4.0 ) 0.1 Powder
AB 1.0 3.9
1st step 1.1 7.8 10
4
)
2nd step 2.6 ) 1.2 10
3
Bulk
HAR 3 1.0 1.0 3.0 0.01 ) Bulk
K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211 203
dried to xerogels at 100C for several days prior to
measurement.
Gels' compositions were determined on the
basis of IR absorption spectroscopy using thin
lm. The absorption coecients of )OC
2
H
5
in
ethanol and )OH in silica glass were used to de-
termine the concentration of these species, as-
suming that those coecients are not changed in
the silica gels.
Pulverized silica xerogels were subjected to
X-ray diraction and
29
Si NMR measurements.
X-ray diraction (XRD) measurements were car-
ried out in a Rigaku Geigerex RAD type h h X-
ray diractometer with Cu Ka and Mo Ka radia-
tions monochromatized by balanced lters and a
graphite monochromator. The scattering intensity,
I S; was measured at intervals of 0.5 in 2h by a
scintillation counter equipped with a pulse height
analyzer, and at least 10 000 counts were accu-
mulated at each angle. After correction for polar-
ization, absorption and background due to the
scattering by air, two scattering curves obtained by
using Cu Ka and Mo Ka radiations were com-
bined to form a single curve. The maximum
S 4p sin h=k; where k is the wavelength of X-
ray) was 140 nm
1
. Scattering intensities were
normalized by Krogh-Moe and Norman's method
combined with high angle method, and then
Fourier transformed to dierential atomic radial
distribution function (d-RDF):
d RDFr
2r
p
Z
S
max
0
S iS expa
2
S
2
sin rS dS;
where r is the interatomic distance in nm,
expa
2
S
2
a damping factor, and
iS IS
obs

X
m
f
2
m

X
m
Z
m

X
j
f
2
mj
! " # ( )
,
f
2
e
;
in which Z
m

P
j
f
2
mj
is a term for Compton
scattering, f
m
and f
e
the scattering factor of the
atom with m electrons and of an electron.
The scattering intensity, I S; was also trans-
formed to the correlation function of electron
density, Cr [12], according to
Cr
1
2p
2
r
Z
S
max
S
min
ISS sin rS dS:
The
29
Si NMR spectra of the silica gels were
measured with a JEOL-EX270 spectrometer at
53.67 MHz using a spin rate of 5000 Hz.
Tetramethyl silane was used as a reference for the
chemical shift of silicon in the gels.
3. Results
Chemical compositions of the silica gels are
given in Table 2. TEOS-silica gels are considered
to contain mostly SiO
2
and SiOH groups.
Fig. 1(a) shows X-ray scattering intensity
curves of the base-catalyzed silica gels and two-
step hydrolysis-silica gel. In the gure, the curves
of the melt-derived silica glass, AR2, AR10 and
HAR3 silica gels are reproduced from the Refs.
[9,11] for comparison. In Fig. 1(b), the magni-
cation of the FSDP positioned at low S value in
Fig. 1(a) is shown for every gel sample. The small
angle scattering, which is caused from the porous
nature of the gels, has been removed in Fig. 1(a)
and (b). The position of FSDP of the silica gels
and melt-derived silica glass in S-value is given in
Table 3. It is seen in Fig. 1(a) and (b), and also in
Table 3 that FSDP of any TEOS-derived silica gel
is at slightly higher S-value than the silica glass,
and that of the HTES-derived silica gel is between
the TEOS-silica gels and the glass.
Dierential radial distribution function, r-RDF
(hereafter abbreviated as RDF), curves of BR3,
BR4 and AB gels, and reference gels and melt-
derived silica glass in the interatomic distance to
Table 2
The chemical composition of the silica gels
Sample Composition (mol%)
OH OC
2
H
5
SiO
2
AR 2 gel 0.38 0.015 0.605
AR 10 gel 0.49 0.001 0.509
BR 3 gel 0.30 ) 0.70
AHR 3 gel
a
SiH
0.50 ) 0.50
a
Nominal composition.
204 K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211
0.8 nm are shown in Fig. 2. Peaks in the RDF
curve of the melt-derived silica glass have been
attributed to dierent atomic pairs as follows: rst
peak around 0.16 nm to Si-1st O neighbors, those
at 0.26, 0.31, 0.4, 0.5, and 0.62 nm to O-1st O,
Si-1st Si, Si-2nd O, the superposition of O-2nd O
and Si-2nd Si, and Si-3rd Si, respectively. Silica
gels exhibit RDF curves which seem to be similar
to the silica glass, however, several dierent points
are to be noted in the RDF curves of gels and
glass. First, the third peak of the gels is smaller in
height than the glass, although it is located at al-
most the same position as in the glass (0.31 nm).
This may indicate that the number density of Si
1st Si pairs in the gels is smaller than in the glass.
Second, a dierence is observed in the peaks at 04
0.5 nm. The peak height ratio of the 0.4 nm-peak
to the 0.5 nm-peak is larger in the gels than in the
glass. Furthermore, the seperation between these
peaks of the gels is slightly smaller than that of the
Table 3
The position of FSDP in the X-ray scattering curves and the
peak separation between 0.4 and 0.5 nm-peaks in the RDF
curves of the silica gels and silica glass
Sample FSDP position (nm
1
) Peak separation (nm)
Silica glass 15.2 0.2 0.096 0.002
AR 2 gel 16.6 0.085
AR 10 gel 16.7 0.083
BR 3 gel 16.6 0.086
BR 4 gel 16.6 0.090
AB gel 16.4 0.089
HAR 3 gel 16.0 0.086
Fig. 1. (a) X-ray scattering intensity curves of the melt-derived silica glass and silica gels made by solgel method under dierent
conditions. (b) FSDP in the X-ray scattering curves of the silica glass and various silica gels.
K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211 205
glass as seen in the gure, and more clearly from
the numerical data given in Table 3. Third, the
RDF peak around 0.62 nm is much reduced in the
gels, compared to the silica glass. As a whole, it is
concluded from the RDF data that the structure in
the distance range from 0.4 to 0.6 nm, or MRO
structure of the ethoxy silane-derived silica gels
diers from the melt-derived silica glass.
In addition, it is important to remark that the
silica gels made under the basis condition and by
the two-step hydrolysis method do not show dif-
ference in X-ray diraction from the gels made
under acidic conditions, and X-ray diraction data
of gels seem not to depend on gel morphology.
Fig. 3 shows the correlation function, Cr;
curves of the silica gels and the silica glass. We
have here the oscillating curves in which the in-
tensity of Cr peak fades with increase of inter-
atomic distance. The peak to peak separation in
the Cr curve provides the periodicity length or
the size of the repeated structure unit in the
amorphous materials, and the convergence point
(in the present study, conveniently dened as a
distance where the peak intensity becomes smaller
than 10% of the most intense peak in a curve)
corresponds to the correlation length or the size of
the primary particle in the case of the gels. The
periodicity and correlation length values derived
for gels and glass are listed in Table 4. The peri-
odicity length or size of the repeated unit in the
gels is seen to be 0.38 nm which is smaller than
that of silica glass. This small dierence is well
reproduced. It should be noted that the periodicity
length of the silica gel is independent of prepara-
tion condition.
The convergence point of the gels is smaller
than that of the glass. Futhermore, it seems that
the base-catalyzed TEOS-derived silica gels has
larger correlation length or the size of the primary
particles than the acid-catalyzed one. Eventually,
Fig. 3. Correlation function curves of the melt-derived silica
glass and various silica gels.
Fig. 2. Dierential RDF curves of the melt-derived silica glass
and silica gels made under dierent conditions.
206 K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211
from the viewpoint of the correlation function, the
dierent MRO of the silica gels from that of the
glass is claried, but dierence in the primary
particle size between the base-catalyzed silica gels
and acid-catalyzed ones is noted.
In Fig. 4,
29
Si NMR spectra of the TEOS-de-
rived and HTES-derived silica gels are shown. The
TEOS-silica gels are seen to be composed of Q
2
,
Q
3
and Q
4
species which are positioned around
)91, )101 and )110 ppm, respectively. Peaks at
about )85 and )110 ppm in the spectrum of the
HTES-silica gel are assigned as so-called T
3
(Si
H) and Q
4
species. Each spectrum was deconvo-
luted to the component peaks, of which chemical
shift and fraction are given in Table 5. Numerical
values in this table are averaged over three mea-
surements. It is seen in Fig. 5 as well as in Table 5
that the fraction of Q
4
is larger in the base-cata-
lyzed silica gels and the gel made by the two-step
hydrolysis method than in the acid-catalyzed silica
gels. However, in base-catalyzed gels the Q
4
frac-
tion is 6070%. Further development of Q
4
species
in the gels was not observed even with increased
amount of hydrolysis water e.g. with R of 50 or
100.
4. Discussion
The RDF curve of the melt-derived silica glass
in the distance range to 0.3 nm has been eluci-
dated with two interconnected SiO
4
tetrahedra
Fig. 4.
29
Si NMR spectra of the silica gels made under dierent
conditions.
Table 5
The chemical shift (ppm) and fraction (%) of Q
2
Q
3
and Q
4
species of the silica gels
Sample Q
2
Q
3
Q
4
(ppm) (%) (ppm) (%) (ppm) (%)
AR 2 gel )93.0 0.2 7 1 )101.0 0.2 56 3 )108.8 0.2 36 3
AR10 gel )92.0 7 2 )101.3 43 1 )110.4 50 2
BR 3 gel )90.8 7 2 )100.9 32 2 )110.2 61 4
BR 4 gel )91.6 3 1 )101.5 29 1 )110.9 68 1
AB gel )91.7 5 1 )101.4 35 1 )110.5 61 1
HAR 3 gel T
2
) 70.5 6 1 T
3
) 85.0 64 2 )111.0 16 2
Q
3
) 101.8 15 1
Table 4
The periodicity length (size of the repeated unit) and the cor-
relation length (primary particle size) of the silica gels
Sample Periodicity length
(nm)
Correlation length
(nm)
Silica glass 0.414 0.002 2.0 0.2
AR 2 gel 0.380 1.2
AR10 gel 0.378 1.2
BR 3 gel 0.379 1.6
BR 4 gel 0.376 1.6
AB gel 0.381 1.2
HAR3 gel 0.393 1.8
K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211 207
having the SiOSi angle of 140150 [13]. RDF
peaks appearing at distance to 0.7 nm is ex-
plainable using MRO structure consisting of the
sixfold siloxane ring which is distorted to the
chair-type (Fig. 5(a)) and with which the silica
glass has been considered to be constructed like
cristobalite and/or tridymite [14]. However, as long
as the glass structure is argued on the basis of X-
ray diraction data, it should be noted that only
average structure information is obtained. Ac-
cordingly, it should be mentioned that the RDF
curve of the silica glass indicates the predominance
of the sixfold siloxane rings in the glass.
As previously reported [8,9] for the acid-cata-
lyzed TEOS-silica gels (AR2 and AR10), silica gels
made under basic condition and/or by two-step
hydrolysis also exhibit some similarity and some
dierences in RDF curves to/from the melt-derived
silica glass. Similarity is observed in the rst peak
in the RDF curve. Namely, its position and area
indicate that BR3, BR4 and AB silica gels also
contain SiO
4
tetrahedral units as the silica glass
does. The presence of the 0.31 nm peak in the
gels implies that SiO
4
tetrahedra are intercon-
nected through making SiOSi bonds by sharing
corner oxygen atoms. However, the smaller peak
height at 0.31 nm in the gels may suggest that
some corner oxygen atoms are not shared by other
tetrahedra, or terminated probably by forming Si
OH bonds. The dierence in the medium inter-
atomic distane (0.40.7 nm) from the silica glass,
i.e., smaller peak separation between the 0.4 and
0.5 nm-peaks, larger peak height ratio of the for-
mer to the latter and the depression of the 0.62
nm-peak could not be explained in terms of the
sixfold siloxane rings.
The dierence in the MRO structure has been
known to be reected on the FSDP in the X-ray
scattering intensity curve [15,16]. As is seen in
Fig. 1(b), FSDP of all silica gels in the present
Fig. 5. Schematic illustration of cyclic siloxane structure units: (a) sixfold siloxane ring (chair-type); (b) fourfold siloxane ring.
208 K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211
study is at a slightly higher S or shorter inter-
atomic distance in real space, which implies that
the MRO structure of the silica gels is more
compact than the silica glass. The higher com-
pactness of the gel than the glass is also inferred
from the smaller peak to peak separation in Cr
curves of the gels or the smaller repeated structure
units than in the glass. Himmel et al. [6,12] pro-
posed a structure unit model which consists of
eight puckered sixfold siloxane ring units in order
to elucidate the higher compactness of MRO
structure of their silica gel, based on FSDP and
correlation function data. Yamana et al. [17] re-
ported growth of the peak around 0.4 nm in their
RDF curve of the silica glass compacted under
high pressure is attributable to Si-2nd Si inter-
atomic pairs in the fourfold siloxane rings
(Fig. 5(b)) which may be induced by pressuriza-
tion. The present authors also tentatively proposed
the structure model consisting of the fourfold si-
loxane ring units for the acid-catalyzed TEOS-sil-
ica gels only on the basis of RDF data. In
modelling the structure units, several other exper-
imental facts that the silica gels exhibit very strong
Raman D
1
peak at 490 cm
1
[8] of which origin
is the fourfold siloxane rings [18], and small IR
band around 550 cm
1
(characteristic of cyclic
tetramers of organosiloxanes) [19], and that cyclic
tetrameric siloxane species are abundant in the
early stage of the hydrolysis of TEOS [3], have
been taken into consideration. Although such a
fourfold siloxane unit is observed only in a limited
number of silicate minerals such as coesite and
feldspars, it is not uncommon in the organ-
osiloxanes.
We, then, extended the X-ray diraction study
to the silica gels made from trifunctional ethoxy
silanes such as CH
3
Si(OC
2
H
5
) and HTES, and
reported that the ladder type siloxane model con-
sisting of fused fourfold siloxane rings (Fig. 6) in
which SiCH
3
or SiH bond is involved as a
terminal group simulates well RDF curves of silica
gels [10,11]. Simulation result for the HTES-silica
gel is reproduced in Fig. 7. Cr function and
29
Si
NMR analyses carried out in the present work
may assist further discussion on the structure
model. As is inferred from the convergence point
of Cr curve shown in Fig. 3, the correlation
length or primary particle size of the HTES-gel is
1.8 nm. This size corresponds to the oligomer
consisting of three or four fused fourfold siloxane
rings. This hexameric oligomer should be termi-
nated by SiH, therefore a very strong peak at
)85 ppm in the
29
Si NMR spectrum (correspond-
ing to T
3
species) is resulted. However, it is con-
sidered that a small number of SiH bonds in the
unit may be attacked to form SiOH bonds
during sol preparation and then condensation re-
action of the SiOH with that in other oligomers
to form SiOSi bridging among particles leads to
the growth of oligomers and nally to the gelation
of the sol. The Si atom interconnecting primary
particles is now Q
4
species and gives rise to a small
peak around )110 ppm in the NMR spectrum.
As can be noticed, the RDF curves of the acid-
catalyzed TEOS-derived silica gels show close re-
Fig. 6. Structure model of the triethoxy silane (HTES)-derived
silica gel based on the fourfold siloxane ring unit.
Fig. 7. RDF observed () for the HTES-silica gel and that
( ) calculated using the structure model shown in Fig. 6
[11].
K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211 209
semblance to that of the HTES-silica gel, sug-
gesting that the above-mentioned MRO model
consisting of the fourfold siloxane rings is also
applicable to these TEOS-derived silica gels. As to
the base-catalyzed, and two-step TEOS-silica gels,
also the resemblance of their X-ray data (FSDP,
RDF and Cr to those of the acid-catalyzed
TEOS-silica gels may lead to the MRO structure
consisting of the fourfold siloxane ring units.
The correlation length of the acid-catalyzed
TEOS-silica gels is read o in their Cr curves to
be 1.2 nm, implying that the primary particles in
these gels correspond to the two fused fourfold
siloxane rings. However, in the case of the TEOS-
gels side groups of the primary particles should be
SiOH which is more feasible for the condensa-
tion reaction. Accordingly a large amount of Si
OSi bridging bonds are formed between primary
particles through the condensation between SiOH
bonds attaching to individual particles, a large
peak around )110 ppm in the NMR spectrum or a
large fraction of Q
4
species being resulted.
In the base-catalyzed TEOS-silica gels, the
correlation length or primary particle size is larger
than the acid-catalyzed ones as seen in Fig. 3,
which is consistent with the Iler's scheme of the
condensation reaction of silicic acid [20]. The si-
loxane oligomer consisting of three or four fused
fourfold rings may form a primary particle. Even
in the base-catalyzed TEOS-silica gels, only 60 to
70% of the SiOH included in a primary particle
was found to be subjected to condensation be-
tween particles to form Q
4
species during gelation.
Any other structure aspects than those observed
in the acid-catalyzed and base-catalyzed TEOS-
silica gels were not discernible in the silica gel
made by the two-step hydrolysis of TEOS. This is
reasonable because any essential dierence in
structure feature between the acid-catalyzed and
base-catalyzed TEOS-silica gels has not been de-
tected.
It is concluded that when silica gel is prepared
from TEOS by the solgel method fourfold silo-
xane ring structure units formed in early stages of
hydrolysis are retained as the skeletal structure
units in the gel, independent of the hydrolysis
condition and/or gel morphology. Higher stability
of the terminated fourfold siloxane ring than the
sixfold siloxane ring has been shown on the basis
of thermodynamic calculation [21]. It, therefore,
may by considered that the terminal groups such
as SiH bonds and SiOH bonds remaining un-
reacted in the HTES-gel and the TEOS-gel stabi-
lize the fourfold siloxane ring in the gels. The
threefold siloxane rings, which have been pointed
out to be also formed in the early stage of the
hydrolysis reaction but by a relatively smaller
amount than the fourfold ones [3], have not been
taken into consideration during modelling the
MRO structure (or skeletal structure) of the silica
gels. This is because Raman D
2
peak which orig-
inates from the threefold siloxane rings was
scarcely observed in the silica xerogels [8]. Even if
this structure unit is retained in the gel, its fraction
should be such that the X-ray technique would not
detect it.
5. Conclusion
1. X-ray scattering intensity, RDF and correlation
functions of all alkoxy-derived silica gels made
under dierent conditions were dierent from
those of the melt-derived silica glass. No sub-
stantial dierence in X-ray data was observed
among those gels. The X-ray data of the silica
gels were explained by using the MRO structure
model consisting of the fourfold siloxane ring
units.
2. Primary particles of acid-catalyzed silica gels
are considered to be made of two fused fourfold
siloxane rings and were 1.0 nm in size, while
those of the base-catalyzed silica gels were
slightly larger.
3. In acid-catalyzed silica gels, the fraction of Si
forming SiOSi bonds (Q
4
species) between in-
dividual primary particles to connect each other
was 4050%. The fraction in the base-catalyzed
silica gel was 6070%.
Acknowledgements
This work was supported by a Grant-in-Aid for
Scientic Research from the Ministry of Educa-
tion, Science and Culture of Japan.
210 K. Kamiya et al. / Journal of Non-Crystalline Solids 240 (1998) 202211
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