Journal of Non-Crystalline Solids 255 (1999) 178184

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Synthesis of MgOSiO2 and CaOSiO2 amorphous powder by

solgel process and ion exchange
Sei-ichi Suda a,*, Toshiya Tashiro a, Takao Umegaki a
a
Department of Applied Chemistry, Graduate School of Engineering, Tokyo Metropolitan University, Minami-Ohsawa 1-1, Hachioji,
Tokyo 192-0397, Japan
Received 14 September 1998; received in revised form 28 April 1999

Abstract
The processing of binary or ternary metaloxide spherical powders often provides ideal starting materials for the
preparation of ceramics or glasses, and the use of these powders can lead to excellent properties. Amorphous spherical
powders composed of SiO2 and MgO or CaO were synthesized by using Na2 OSiO2 spherical powder as a starting
material and then conducting ion-exchange between the magnesium or calcium ions and the sodium ions in the Na2 O
SiO2 powder. The maximum amount of magnesium or calcium in the powder was Mg/Si 0.5 or Ca/Si 0.8. The ratios
of Mg/Si and Ca/Si were then determined by controlling the alkaline-earth concentration of the suspension used for the
ion exchange. The ratio of Mg2 or Ca2 to consumed Na as a result of the ion exchange was estimated to be 1.0, and
it was found that OH around SiONa also participates in the ion exchange. The ratio of water to ethanol in the
reaction mixture also inuenced the ion exchange. 1999 Elsevier Science B.V. All rights reserved.

1. Introduction or ternary metal oxide spherical powders because

Spherical particles can be eectively obtained
by the solgel methods [1,2]. Solgel processing
also allows us to prepare such powders rather
easily and inexpensively because no large or special
instruments are required. Stober and Fink have
successfully prepared mono-dispersed TiO2 and
SiO2 powders, and the St ober method, which is a
kind of solgel method, has been very popular and
indispensable for producing spherical powders [3
6]. However, the St ober method is, in principle,
restricted to single metal oxide powders such as
TiO2 and SiO2 , and it is dicult to obtain binary
*
Corresponding author. Tel.: +81-426 77 2826; fax: +81-426
77 2821; e-mail: suda-seichi@c.metro-u.ac.jp
0022-3093/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 9 9 ) 0 0 3 7 0 - 1
of aggregation and compositional inhomogene-
ities. Binary or ternary oxide spherical powders,
however, would be very useful for processing ce-
ramics [7,8].
In our study on solgel processes, we found that
the reaction between Si alkoxide and alkali ions
can occur by controlling both the proton and al-
kali ion concentrations in the reaction mixture [9
11]. The reaction is composed of two processes: (1)
hydrolysis of the Si alkoxide, which leads to the
formation of SiOH, and (2) ion exchange between
alkali ions and protons of SiOH, which leads to
the formation of bonds similar to SiOA (A: al-
kali metal). Both the hydrolysis and the ion
exchange are inuenced by the proton and alkali
ion concentrations in the reaction mixture, and
both the concentrations appear to aect the
 S.-i. Suda et al. / Journal of Non-Crystalline Solids 255 (1999) 178184
concentration of SiOA bonds in the oligomer.
We have previously obtained Na2 OSiO2 amor-
phous spherical powder (NS powder) by means of
the reaction that includes the hydrolysis and the
alkali ion exchange [12].
In this study, spherical powders of amorphous
silicate, MgOSiO2 and CaOSiO2 , were synthe-
sized; this kind of synthesis is important because
alkaline earth silicates are used in plate glass and
Fig. 1. Scheme for MOSiO2 (M: Mg or Ca) spherical powder
by ion exchange.
179
ber glass products, and the amorphous structure
can make possible the preparation of glasses at
relatively low temperatures. Ion exchange between
alkaline earth ions and the protons of SiOH had
been previously investigated, but we could not nd
suitable conditions for promoting direct ion ex-
change between alkaline earth ions and the pro-
tons of SiOH. Therefore, amorphous Na2 OSiO2
powders were used for the preparation of MgO
SiO2 and CaOSiO2 spherical powders (CS and
MS powders, respectively). Ion exchange between
the alkaline earth ions and sodium in the NS
powder led to the formation of SiOM (M: al-
kaline earth), resulting in the production of
amorphous CaOSiO2 and MgOSiO2 spherical
powders (Fig. 1). NS powders were soaked into
suspensions composed of water, ethanol and al-
kaline earth ions. The suspensions with various
concentrations of alkaline earth ions and various
ratios of water solution to ethanol (s/e) were pre-
pared. The eects of both the concentrations and
the s/e ratio on the ion exchange were investigated
in order to nd suitable synthesis conditions for
preparing CS and MS spherical powders.
2. Experimental
The NS powders used as starting powders were
prepared as follows. A solution of tetraethyl-
orthosilicate (TEOS), ethanol, hydroxypropyl cel-
lulose (HPC) [13] and water (pH 3.0) was
prepared and stirred at 40C for 40 min in dry N2 .
Another solution composed of ethanol, water and
NaOH was prepared, where the sodium and proton
concentrations were set to adequate values, and
poured into the TEOS solution. The molar ratio of
[TEOS]:[NaOH]:[H2 O]:[ethanol] in the mixed so-
lution was set to 1:x:2.0:50, with x ranging from 0.0
to 1.6. The concentration of HPC in the mixed
solution was also set to 6.0 101 g dm3 . After
stirring for 40 min, wet gel powders resulted from
the hydrolysis reaction and the ion exchange, and
these powders were separated from the mixed so-
lution by ltration through a membrane lter with
0.1 lm pores. The powders were washed with eth-
anol and freeze-dried. The mole ratio, Na/Si, of the
obtained NS powder was controlled from 0.0 to 0.8
180 S.-i. Suda et al. / Journal of Non-Crystalline Solids 255 (1999) 178184
Fig. 2. Flow chart for the preparation of non-crystalline MO
SiO2 (M: Mg or Ca) powder.
by employing suitable sodium and proton con-
centrations in the mixed solution. The XRD mea-
surement showed that the NS powder was
amorphous. The NS powder with a Na/Si ratio of
0.7 was used for the following experiments.
Fig. 2 shows a ow chart for the preparation of
CS and MS powders. The NS powder was added
to a suspension of ethanol, water, hydroxypropyl
cellulose, HNO3 or NH4 OH, and Ca(NO3 )2 or
Mg(NO3 )2 , and the resultant suspension was stir-
red at 40C for 24 h in air in order to promote the
ion exchange between the calcium or magnesium
ions and sodium within the NS powder. The ob-
tained CS or MS powder was separated from the
suspension by ltration through a membrane lter
with 0.1 lm pores, washed with ethanol several
times, and dried with a freeze-dryer. Scanning
electron microscopy (SEM) was applied to eluci-
date the morphology and distribution of particle
size, and energy-disperse X-ray spectroscopy
(EDS) was used to determine the composition of
the MS and CS powders. The composition of the
powders was estimated as the average of at least
ve measurements, and the errors of the compo-
sition were estimated to be within 6%.
3. Results
3.1. MgO/Na2 OSiO2 powder
The pH values of all the magnesium solutions
with various concentrations of magnesium were
adjusted to 10.0 using HNO3 , NH4 OH and water.
The suspension of the magnesium solution (2 ml)
and ethanol (58 ml), which was estimated to be
s/e 3.5 vol.%, was prepared for the magnesium
ion exchange. After the addition of NS powder,
the suspension was stirred at 40C for 24 h in air.
The obtained MS powder was separated by l-
tration, washed with ethanol and dried with a
freeze-dryer. Fig. 3 shows the eects of magnesium
concentration in the suspension on the Na/Si and
Mg/Si ratios in the MS powder. The Mg/Si and
Na/Si ratios of the obtained MS powder were es-
timated by EDS. The Mg/Si ratio increased with
increases in the magnesium concentration of the
suspension; a suspension with a magnesium con-
centration of more than 0.1 mol dm3 resulted in
an amorphous silicate powder with compositions
of Mg/Si 0.5 and Na/Si 0.1. These results show
that alkaline-earth ion exchange for sodium in NS
powder does occur and that suspensions with
various magnesium concentrations make it possi-
ble to obtain MS powder with various amounts of
magnesium.
The eect of the pH of the magnesium solution
on the Mg/Si and Na/Si ratios in the MS powder
was investigated to extend the range of the Mg/Si
ratio in the MS powder. MS powder was prepared
using a suspension with ethanol and magnesium
solution. The concentration of magnesium in the
suspension was adjusted to 0.2 mol dm3 . Fig. 4
Fig. 3. The relationship between the magnesium concentration
in the suspension and the Mg/Si and Na/Si ratios of the pow-
ders. (d) and (n) represent Na/Si and Mg/Si, respectively.
 S.-i. Suda et al. / Journal of Non-Crystalline Solids 255 (1999) 178184
Fig. 4. The relationship between the pH of the magnesium
solution and the Mg/Si and Na/Si ratios of the powders. (d)
and (n) represent Na/Si and Mg/Si, respectively.
shows the relationship between the pH of the
magnesium solution and the Na/Si or Mg/Si ratio
in the obtained MS powder. The pH of the mag-
nesium solution ranged from 8.0 to 12.5. The
composition of the MS powder was independent
of the pH of the magnesium solution. Magnesium
ion exchange for sodium was found to be inde-
pendent of [H ] or [OH ] at a pH range of 8.0
12.5 in the suspension. Control of pH does not
lead to an extension of the composition range in
the MS powder.
The reaction time dependence on the composi-
tion of MS powder was also investigated to de-
termine the rate of the ion exchange. The pH of the
magnesium nitrate solution was adjusted to 10.0,
and the concentration of Mg (NO3 )2 in the sus-
pension to 0.2 mol dm3 . The MS powders were
synthesized by soaking in the suspension at 0.0C
for less than 10 s, 5, 10, 15 and 20 min. Fig. 5
shows the time dependence of the Mg/Si and Na/Si
ratios in the MS powder. The MS powder syn-
thesized through the ion exchange conducted for
less than 10 s had almost the same Mg/Si ratio as
that of a 24-h ion exchange, while the Na/Si ratio
decreased with increases in the reaction time and
reached Na/Si 0.1 after 20 min. The magnesium
ion exchange was thus fast enough to be complete
in less than 10 s.
181
Fig. 5. The time dependence of the ratios of Mg/Si and Na/Si in
the MS powders. (d) and (n) represent Na/Si and Mg/Si, re-
spectively.
3.2. CaO/Na2 OSiO2 powder
The pH values of all the calcium solutions with
various calcium concentrations were also adjusted
to 10.0 with HNO3 , NH4 OH, and water. NS
powder was added to the suspension of the cal-
cium solution (2 ml) and ethanol (58 ml), which
was estimated to be s/e 3.5 vol.%, and the sus-
pension was stirred at 40C for 24 h in air. The
eect of the calcium concentration on the Ca/Si
and Na/Si ratios in the obtained CS powder is
shown in Fig. 6. The Ca/Si ratio increased with
increases in the calcium concentration of the
suspension, but the slope of the curve was reduced
when the suspension with calcium at a concen-
tration of more than 0.05 mol dm3 was used. It
appears to be possible to change the composition
of the CS powder by controlling the calcium
concentration of the suspension, but the compo-
sition range of the CS powder was narrow relative
to that of the MS powder. The maximum Ca/Si
ratio of the CS powder prepared using the sus-
pension of s/e 3.5 vol.% was Ca/Si 0.3 with
Na/Si 0.3.
The ratio of the calcium solution to ethanol in
the suspension was then changed to extend the
available range of the Ca/Si ratio in the CS
powder. Fig. 7 shows the Ca/Si and Na/Si ratios
182 S.-i. Suda et al. / Journal of Non-Crystalline Solids 255 (1999) 178184
Fig. 6. The relationship between the calcium concentration of
the suspension with s/e 3.5 vol.% and the Ca/Si and Na/Si
ratios of the powders. (d) and (n) represent Na/Si and Ca/Si,
respectively.
Fig. 7. The relationship between the calcium concentration of
the suspension with s/e 9.1 vol.% and the Ca/Si and Na/Si
ratios of the powders. (d) and (n) represent Na/Si and Ca/Si,
respectively.
of the CS powders prepared with a suspension of
the solution (5 ml) and ethanol (55 ml), which
was estimated to be s/e 9.1 vol.%. The Ca/Si
ratio increased with increases in the calcium
concentration of the suspension, and there was no
tendency for the Ca/Si ratio to saturate. The use
of the suspension with a calcium concentration
of 0.6 mol dm3 resulted in a CS powder
containing calcium at a Ca/Si ratio of 0.8. The
range of the Ca/Si ratio was extended by in-
creasing the s/e ratio. A suspension of 10 ml of
the calcium solution and 50 ml of ethanol
(s/e 20 vol.%) was then employed in order to
obtain CS powder with a higher concentration of
calcium. However, the Ca/Si ratio was saturated
again with a calcium concentration of more than
0.05 mol dm3 , and the Ca/Si ratio was limited to
0.5 (Fig. 8).
Fig. 9 shows SEM photographs of the NS
powder that was used as a starting powder as well
as CS powders with compositions of Ca/Si 0.6
and Na/Si 0.2. The CS powder had a similar
particle size to the NS powder, and the average
particle size of the CS powder was observed to be
0.30.4 lm. However, the CS powder exhibited
some aggregation. The CS powder was aggregated
while soaking in the suspension and it is therefore
necessary to investigate the conditions of the sus-
pension precisely to obtain mono-dispersed, ag-
gregation-free CS and MS powder.
Fig. 8. The relationship between the calcium concentration of
the suspension with s/e 20 vol.% and the Ca/Si and Na/Si
ratios of the powders. (d) and (n) represent Na/Si and Ca/Si,
respectively.
 S.-i. Suda et al. / Journal of Non-Crystalline Solids 255 (1999) 178184
Fig. 9. SEM photographs of the Na2 OSiO2 powder as a
starting powder (a) and the CaOSiO2 powder prepared with
the suspension with s/e 9.1 vol.% (b).
4. Discussion
4.1. The ratio of magnesium or calcium to consumed
sodium by ion exchange
Amorphous silicate powders containing alka-
line earth metals were prepared by ion exchange
for sodium in NS powder. The eects of the proton
or magnesium ion concentration and the s/e ratio
on the magnesium ion exchange were investigated
in order to determine the appropriate conditions
for obtaining MS powder. The results showed that
the Mg/Si ratio of the MS powder is independent
of s/e ratio and pH at a pH range of 8.012.5, and
the Mg/Si ratio is dependent only on the magne-
sium concentration of the suspension. The ion
exchange between sodium and magnesium in the
amorphous silicate powder would be complete
183
within 10 s, as was indicated by the Mg/Si ratio
being unchanged with time after 10 s. On the other
hand, the Na/Si ratio decreased with time and
reached approximately Na/Si 0.1 after 20 min.
The decrease in the Na/Si ratio after 10 s arose
from the dissolution of sodium out of the NS
powder into the suspension and not from con-
sumption by ion exchange, because the decrease
continued after the ion exchange was completed.
NS powder containing the same Na/Si ratio was
used to prepare MS powder and the soaking time
in the suspension was set to 24 h. It was then as-
sumed that the amount of sodium dissolved in the
suspension was identical to Na/Si 0.1. According
to this assumption, the Na/Si ratio in the NS
powder decreased from 0.7 to 0.2 in response to
the magnesium ion exchange, and the Mg/Si ratio
increased from 0.0 to 0.5 (Fig. 3). The Na/Si ratio
in the NS powder consumed by the ion exchange
was estimated to be 0.5, and the Mg/Si ratio gen-
erated simultaneously was also estimated to be 0.5.
Therefore, the ratio of generating magnesium to
consumed sodium was estimated to be 1.0.
The ratio of calcium to consumed sodium by
ion exchange was also estimated according to the
assumption that sodium in the MS powder was
dissolved in the suspension at a Na/Si ratio of 0.1.
The ratio of calcium to sodium was then estimated
using the results in Fig. 6. The Na/Si ratio in the
NS powder decreased from 0.7 to 0.4 by ion ex-
change, and the Ca/Si ratio simultaneously in-
creased from 0.0 to 0.3. The ratio of generating
calcium to consumed sodium by ion exchange was
also estimated to be 1.0. The ratio indicates that
ion exchange between univalent and divalent cat-
ions would occur at a rate of 1.0. The suspension
around SiONa was basic and contained a large
amount of OH . Therefore, the ion exchange
would occur according to Eq. (1), and OH
around SiONa would be essential to promoting
the ion exchange.
Na $ Ca2 OH : 1
4.2. The eects of s/e ratio
The amount of alkaline earth metals in
the obtained CS powder was much inuenced by
184 S.-i. Suda et al. / Journal of Non-Crystalline Solids 255 (1999) 178184
the s/e ratio of the suspension as compared with
that in the MS powder. The Mg/Si ratio in the MS
powder appeared to be saturated in terms of the
magnesium concentration when the MS powder
was prepared using the suspension containing
magnesium at a concentration of more than 0.1
mol dm3 . The ratio of Ca/Si also appeared to be
saturated when the suspension with s/e 3.5 vol.%
contained calcium at a concentration of more than
0.1 mol dm3 . When the suspension with s/e 9.1
vol.% was employed, the Ca/Si ratio then in-
creased with increases in the calcium concentration
in the suspension, and the ratio was not saturated
in terms of the calcium concentration. The sus-
pension containing ethanol at a ratio of s/e 9.1
vol.% and a calcium concentration of 0.6 mol
dm3 resulted in CS powder with a Ca/Si ratio of
0.8. However, saturation of the Ca/Si ratio was
observed again when the suspension with an s/e
ratio of more than 9.1 vol.% was used to prepare
the CS powder.
The reaction of the ion exchange between cal-
cium and sodium was much inuenced by the state
of the calcium in the suspension composed of
water and ethanol because the calcium ion ex-
change for sodium depended on the s/e ratio. The
Ca/Si ratio did not become saturated in terms of
the calcium concentration when CS powder was
prepared using the suspension with s/e 9.1 vol.%,
and CS powder with various concentrations of
calcium was obtained by employing a suspension
with s/e 9.1 vol.%. The use of a suspension with
s/e 9.1 vol.% appears to provide optimal condi-
tions for preparing CS powder. Thus, a more
precise investigation of the state of alkaline earth
ions in the suspension would lead to an extension
of the available range of composition in mono-
dispersed spherical powders.
5. Conclusion
Amorphous alkaline-earth silicate powders
were prepared by the solgel process and ion ex-
change. MS or CS powder was obtained using NS
powder as a starting material and conducting
magnesium or calcium ion exchange for sodium in
the NS powder. The alkaline earth compositions
of the obtained MS and CS powders were con-
trolled by using suspensions with varying amounts
of alkaline earth metals. The maximum ratio of
alkaline earth metals in the obtained MS and CS
powders were Mg/Si 0.5 and Ca/Si 0.8, re-
spectively. The ratio of alkali earth metals to
consumed sodium by ion exchange was estimated
to be 1.0. Therefore, the OH around SiONa
appears to participate in the ion exchange between
the alkaline earth ions and sodium in the NS
powder. The dependence of the Ca/Si ratio on the
s/e ratio of the suspension composed of the water
solution and ethanol was also dierent. Therefore
we found it essential to investigate not only the pH
or cation concentration in the suspension but also
the s/e ratio to obtain mono-disperse spherical
powder with various amounts of alkaline earth
metals.
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