Eects of aging and drying conditions on the structural

and textural properties of silica gels

Juncal Estella
a
, Jesu s C. Echeverr a
a
, Mariano Laguna
b
, Julian J. Garrido
a,
*
a
Departamento de Qumica Aplicada, Universidad Pu blica de Navarra, Campus Arrosad a, 31006 Pamplona, Spain
b
Instituto de Ciencia de Materiales de Arago n, CSIC, Universidad de Zaragoza, Campus de Plaza San Francisco, 50009 Zaragoza, Spain
Received 3 October 2006; received in revised form 4 January 2007; accepted 5 January 2007
Available online 17 January 2007
Abstract
Solgel derived materials are widely used as porous matrices for preparing optical chemical sensors or biosensors. The porosity of the
support matrix is a key variable that aects the sensitivity and response time of the sensors. The aim of this research is to study the eect
of dierent aging and drying conditions on the structure and porosity of silica gels to obtain materials of tailored porosity. The gels were
aged in ethanol or NH
3(aq)
(0.5 M and 2.0 M), and dried under atmospheric (xerogels) or supercritical conditions for ethanol (aerogels).
Aging and drying conditions strongly aected the porous texture of silica gels. The surface area and micropore volume was higher in
xerogels than in aerogels. Xerogel aged in ethanol was mainly microporous, while xerogels aged in ammonia were mesoporous due
to cross-linking reactions in alkaline media. The maximum from the BJH distribution appeared at 4.0 nm for the xerogel aged in
0.5 M NH
3(aq)
and at 5.4 nm for the xerogel aged in 2 M NH
3(aq)
. Aerogels were macroporous materials, and macropore volume con-
stituted over 92% of the total pore volume, independently of the aging media. Esterication reactions inside the reactor promoted cross-
linking, which resulted in a higher skeletal density and an increase in the absorbance of SiO related IR bands. Cross-linking strengthens
the gel network and reduces the amount of shrinkage under atmospheric conditions. SEM and TEM micrographs conrmed the textural
properties of xero- and aerogels deduced by gas adsorption, Hg porosimetry and density measurements.
2007 Elsevier Inc. All rights reserved.
Keywords: Xerogels; Aerogels; Aging; Supercritical drying; Porous texture
1. Introduction
The use of the solgel process to produce materials for
optical chemical sensors and biosensors is attracting con-
siderable research interest. The main advantages of porous
silica are its transparency and its chemical and thermal sta-
bility [1]. In most applications, the solgel derived material
provides a porous support matrix in which analyte-sensi-
tive species are entrapped and into which analyte molecules
may diuse and interact. The porosity of the matrix plays a
key role in determining the sensitivity and response time
of such optical sensors [2] because the diusion coecient
for the analyte through the matrix increases with lm
porosity [3].
Several parameters such as the chemical precursor, sol-
vent composition, pH, and temperature aect hydrolysis
and condensation reactions, and therefore the porous tex-
ture of silica gels [4]. In general, acid-catalyzed hydrolysis
and condensation lead to weakly branched and micropo-
rous structures, whereas basic conditions or two step
acidbase processes increase cross-linking, leading to
decreased microporosity and a broader distribution of lar-
ger pores in silica gels [57].
Aging and drying also aect the pore structures of silica
gels. Vega and Scherer [8] demonstrated that condensation
in silica gels continues long after gelation due to the large
concentration of labile hydroxyl groups. By creating new
bonds bridging separate chains, polymerisation reactions
1387-1811/$ - see front matter 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.01.007
*
Corresponding author. Tel.: +34 948 169601; fax: +34 948 169606.
E-mail address: j.garrido@si.unavarra.es (J.J. Garrido).
www.elsevier.com/locate/micromeso
Microporous and Mesoporous Materials 102 (2007) 274282
stien and strengthen the network. The aging solution and
pH also aect the dissolution and reprecipitation of silica,
which is called coarsening or Ostwald ripening [9,10].
Drying involves the loss of water, alcohol and other vol-
atile components. During drying under atmospheric condi-
tions, the gel initially shrinks due to the loss of pore uid
maintaining the liquidvapour interface at the exterior sur-
face of the gel. At the nal stage of drying, liquidvapour
menisci recede into the gel interior [10]. By transforming
the solvent into a supercritical uid, surface tension disap-
pears along with the capillary pressure gradient built up in
the pore walls, avoiding the potential collapse of the pore
volume due to capillary forces. Supercritical drying leaves
the porous texture of the wet gel intact by avoiding pore
collapse, and the resulting materials are generally hydro-
phobic since their surfaces are covered with alkoxy groups
[11].
The aim of this research was to study the eect on the
structure and porosity of silica gels of aging in ethanol or
NH
3(aq)
(0.5 M and 2 M), and drying under atmospheric
(xerogels) or supercritical conditions for ethanol (aerogels).
An alcogel obtained in acidic media with a gelation time of
5 h was used as a reference, which resulted in a micropo-
rous xerogel when aged in ethanol for a week and dried
under atmospheric conditions. This alcogel is appropriate
for studying the eects of aging and drying conditions on
the textural properties of silica gels. Starting from tetraeth-
ylorthosilicate (TEOS) hydrolysis in acid media and con-
trolling aging and drying conditions, micro-, meso- and
macroporous materials were synthesized to be used as sup-
port matrices for optical chemical sensors.
2. Materials and methods
2.1. Synthesis of xerogels and aerogels
Preparation of silica alcogels using the solgel process
has been well described in the literature and will be briey
mentioned here. TEOS was obtained from Fluka (Switzer-
land) with purity greater than 98%. Merck (Darmstad,
Germany) supplied hydrochloric acid and GR absolute
ethanol for analysis, and water was MilliQ quality. TEOS
and ethanol were mixed in a 1:4.75 molar ratio with a mag-
netic stirrer. While stirring, water was added dropwise until
a TEOS:water molar ratio of 1:5.5 was achieved, and the
pH of the solution was adjusted at 4.5 by adding 0.05 M
HCl with an automated burette (Titrino 702 SM, Metr-
ohm, Herisau, Switzerland). Sample containers were closed
and kept until gelation in an orbital shaker.
Alcogels were covered with 5 mL of the aging solvent
(ethanol, 0.5 M or 2.0 M aqueous ammonia) and allowed
to age for 7 days. Four samples were prepared for each
aging solvent. Half of the alcogels were dried at atmo-
spheric pressure and room temperature to obtain xerogels.
Glass containers were covered with paralm
TM
with several
needle holes to allow for the evaporation of the aging
solvent.
The other half of the alcogels was dried under supercrit-
ical conditions for ethanol (516 K and 63 bar). Before
supercritical drying, alcogels aged in ammonia were
washed four times with 5 mL ethanol over 2 days to
remove water prior to drying, since removing water under
supercritical conditions leads to silica dissolution.
For supercritical drying, each 40 mL glass ask contain-
ing an alcogel was placed in an autoclave with 160 mL
capacity (Mod. 4842, Parr Instrument Company, IL,
USA). Ethanol (40 mL) was added, approximately 15 mL
to the ask and the rest to the body of the autoclave. This
drying procedure has been found to be the key to obtaining
crack-free monolithic aerogels, because it prevents the ini-
tial evaporation of the solvent from the gel during heating
[12].
After tight closing, the autoclave was ushed with N
2
and then pre-pressurized above 100 bar. The temperature
of the autoclave was increased to 573 K at a maximum rate
of 7 K min
1
. After stabilization at the maximum temper-
ature and pressure, the vapour outlet micrometering valve
of the autoclave was slowly opened to vent out the solvent.
All the solvent was evacuated from the autoclave at 573 K
in about 2 h. After reaching atmospheric pressure, the heat
was turned-o to cool down the reactor, and nally the
autoclave was ushed with N
2
at 2 bar.
2.2. Characterization of xerogels and aerogels
Skeletal density was measured by helium pycnometry
(Accupyc 1330, Micromeritics, Norcross, GA), and bulk
density was obtained by mercury pycnometry (Poresizer
9320, Micromeritics). FTIR spectra were obtained using
a Nicolet Avatar 360 FTIR spectrometer (Madison,
USA). For each sample, 32 scans in the 4000400 cm
1
spectral ranges were recorded with a resolution of
4 cm
1
. The KBr pressed-disc technique was used at two
sample concentrations with 2 or 0.6 mg of the gel dispersed
in 200 mg KBr to record spectra in the regions of 4000
2200 and 2200400 cm
1
, respectively. Discs were heated
in a furnace overnight at 423 K to minimize water adsorp-
tion [13].
Nitrogen (77 K) and CO
2
(273 K) adsorption were per-
formed using an ASAP 2010 volumetric adsorption ana-
lyzer (Micromeritics). Approximately 100200 mg of each
sample was accurately weighed out in an elongated Pyrex
glass tube. Before the adsorption analysis, the samples were
outgassed for at least 15 h at 423 K in the degas port of the
adsorption apparatus, with residual vacuum less than
6.7 10
6
lbar.
Scanning electron microscopy (SEM) images were
obtained on a JEOL JSM 6400 mod. 6210 microscope
(Oxford, United Kingdom). Samples were placed on brass
cylinders, dried in a vacuum chamber at room temperature
and covered with a gold layer. Transmission electron
microscopy (TEM) analysis was done on a JEOL-2000
FXII. A small amount of sample powder was dispersed
in ethanol using an ultrasound bath.
J. Estella et al. / Microporous and Mesoporous Materials 102 (2007) 274282 275
3. Results and discussion
Sample morphology depended on the conditions of
aging and drying. Aerogels maintained the original alcogel
size and hardly displayed cracks, whereas xerogels shrunk
and were monolithic in some cases but had cracks in other
cases due to capillary pressure. Xerogel aged in ethanol
were transparent, while xerogels aged in ammonia were
translucent and had a rugged surface, probably due to
the re-dissolution of silica that takes place in alkaline pH.
Among aerogels there were little dierences based on the
aging solvent. Aerogels were transparent with a bluish
color, although they appeared yellow depending on the
incident angle of the light. Heterogeneity on the nanometer
scale is responsible for Rayleigh scattering which makes the
sample appear yellowish when light is observed by trans-
mission through it but bluish when light is observed by
reection against a dark background [11].
3.1. Skeletal and bulk density
Mean skeletal density values (q
He
) obtained from helium
pycnometry and bulk density (q
Hg
) values deduced from
mercury pycnometry are presented in Table 1. For each
given sample, skeletal density is higher than bulk density,
but this dierence is much larger for aerogels than for xero-
gels. Under atmospheric pressure, alcogels shrink during
drying leading to an increase in the bulk density, but alco-
gels contract very little under supercritical conditions,
yielding an extremely low bulk density.
The skeletal density of aerogels is larger than that of
xerogels because during aerogel preparation, esterication
reactions inside the reactor promote cross-linking by con-
densation, producing a more dense structure [4,14]. Sam-
ples aged in NH
3(aq)
have a larger skeletal density than
samples aged in ethanol. Aging in NH
3(aq)
favours further
hydrolysis and condensation processes that increase skele-
tal density.
The volume fraction of porosity (V
v
) [6] was calculated
using the relation
V
v
1
q
Hg
q
He

100 1
The results of the volume fraction of porosity show that
xerogels aged in ethanol have the lowest porosity
(20.7%), which increases to 50% when xerogels are aged
in NH
3(aq)
(Table 1). Aerogels have a volume fraction of
porosity above 92% independent of the aging media.
3.2. Infrared spectroscopy
Figs. 1 and 2 show the infrared spectra of xero- and
aerogels, respectively, aged in ethanol, 0.5 M or 2 M aque-
ous ammonia solution. In the 40002800 cm
1
range, the
absorption band near 3440 cm
1
stands out and can be
attributed to the stretching modes of residual SiOH and
some adsorbed water [15]. In general, the intensity of this
band reects the amount of residual SiOH, which is inver-
sely related to the degree of condensation [16]. This band is
often accompanied by another at 1630 cm
1
, which is
attributed to the OH vibrations of molecular water that
is physically adsorbed in the network. Because of the low
intensity of the peak at 1630 cm
1
, the 3440 cm
1
band
mostly reects silanol groups. The intensity of this band
is larger in aerogels than in xerogels. In xerogels, the
3440 cm
1
band is more intense in samples aged in ammo-
nia solution than in those aged in ethanol.
Bands near 2980, 2935 and 2905 cm
1
(Figs. 1a and 2a)
are assigned to CH stretching and deformation vibrations
from the ethoxy groups (OC
2
H
5
), and they are also more
intense in aerogels than in xerogels, where they almost dis-
appear independent of the aging medium. According to
Table 1
Density and porosity of xero- and aerogels aged in dierent media
Aging Skeletal
density
a
/g cm
3
Bulk
density
b
/g cm
3
Volume fraction
of porosity/%
Xerogels
Ethanol 1.631 1.294 20.7
0.5 M NH
3
1.968 0.991 49.6
2.0 M NH
3
2.012 0.993 50.7
Aerogels
Ethanol 2.158 0.163 92.4
0.5 M NH
3
2.521 0.133 94.7
2.0 M NH
3
2.589 0.136 94.7
a
Obtained by helium pycnometry.
b
Obtained by mercury pycnometry.
800 1000 1200 1400 1600 1800 2000
0.5 M - NH3
2 M - NH3
EtOH
1090
800
460
400 600
3000 3200 3400 3600 3800 4000
Wavenumber (cm
-1
)
Wavenumber (cm
-1
)
2 M - NH
3
0.5 M - NH
3
EtOH
2980
3440
2935
a
b
Fig. 1. Infrared spectra of xerogels in two wavenumber ranges: (a) 4000
2800 cm
1
and (b) 2000400 cm
1
.
276 J. Estella et al. / Microporous and Mesoporous Materials 102 (2007) 274282
Bertoluzza et. al. [17], these bands result from the incom-
plete hydrolysis of TEOS. They have also been attributed
to the reaction of the silanol groups with ethanol under
supercritical conditions [11], in particular, the esterication
of the silica surface by the alkyl groups of ethanol in the
reactor [14]. To test this esterication hypothesis, a xerogel
sample aged in ethanol that did not have bands in the range
of 29802905 cm
1
was dried under supercritical condi-
tions. The presence in aerogels of new CH bands corre-
sponding to ethoxy groups conrms that esterication
reactions with the formation of alkoxy groups take place
inside the reactor during the drying process (Fig. 3).
Figs. 1b and 2b show the infrared spectra of the 2200
400 cm
1
range of xero- and aerogel samples aged in the
three media. The most intense peak is observed at
1090 cm
1
in xerogels and at 1105 cm
1
in aerogels due
to the asymmetric stretching vibration of the SiO bond
that makes up the skeletal SiO
2
network [9]. The absor-
bance of this peak for aerogels is around three times the
intensity of that for xerogels. This band goes together with
two bands around 800 cm
1
and 470 cm
1
which are
assigned, respectively, to bond bending and bond rocking
vibrations of the SiO bonds in the three-dimensional
SiO
2
network. The larger absorbance of bands correspond-
ing to SiO bonds in aerogels seems to be related to the
increase in skeletal density and suggests that supercritical
drying enhances cross-linking through condensation
reactions.
3.3. Porous texture
Fig. 4a shows the N
2
adsorptiondesorption isotherms
(77 K) of xerogels aged in ethanol and NH
3(aq)
. According
to IUPAC classications, the adsorption branch of the
xerogel aged in ethanol corresponds to type I, and is char-
acteristic of microporous solids. The small hysteresis loop
is typical of type IV isotherms obtained from mesoporous
materials [18]. Using an ammonia solution for aging
3000 3200 3400 3600 3800 4000
Wavenumber (cm
-1
)
EtOH
0.5 M- NH
3
2 M- NH
3
3440
2980
2935
2905
2800
600 1000 1400 1800 2200

Wavenumber (cm
-1
)
0.5 M - NH
3
2M - NH
3
EtOH
1105
800
470
970
a
b
Fig. 2. Infrared spectra of aerogels in two wavenumber ranges: (a) 4000
2800 cm
1
and (b) 2200400 cm
1
.
AE
XG
3
4
4
3
2
9
0
4
2
9
3
4
2
9
8
4
2800 3000 3200 3400 3600 3800 4000
Wavenumbers (cm
-1
)
Fig. 3. Infrared spectra of a xerogel (XG) before and the corresponding
aerogel (AE) after supercritical drying.
0
5
10
15
20
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
/

m
m
o
l

g
-
1
XG-EtOH XG- 0.5 M NH3 XG-2 M NH3
0
20
40
60
0 0.2 0.4 0.6 0.8
p/p
0
n
a
/

m
m
o
l

g
-
1
AE-EtOH AE-0.5 M NH3 AE-2 M NH3
0
2
4
6
8
0 0.1 0.2
b
a
1
Fig. 4. Adsorptiondesorption isotherms of N
2
at 77 K of (a) xerogels and
(b) aerogels aged in ethanol and NH
3(aq)
.
J. Estella et al. / Microporous and Mesoporous Materials 102 (2007) 274282 277
xerogels results in isotherms of type IV with a H2 hysteresis
loop, associated with the lling and emptying of mesopores
through capillary condensation. In the mesopore region, in
the relative pressure (p/p
0
) range between 0.30 and 0.90, N
2
adsorption increased with NH
3(aq)
concentration and the
adsorptiondesorption branches of the hysteresis loop
shifted towards a higher relative pressure. The sample aged
in 2 M ammonia solution had a larger hysteresis loop than
the sample aged in 0.5 M, which indicates that increasing
the ammonia concentration in the aging solution results
in a larger volume and diameter of mesopores.
Independently of the aging media, N
2
adsorption
desorption isotherms of aerogels were of type IV according
to the IUPAC classications (Fig. 4b). Compared to the
corresponding xerogel isotherms, aerogels contain over
twice the pore volume, and pore sizes are much greater
as is evident from the larger amount of adsorption that
occurs at relative pressures above 0.90. The pores in aero-
gels mainly consist of macropores which are attributed to
the interstices between the grains [4]. The aerogel aged in
ethanol has a hysteresis loop type H2 with a limiting value,
whereas those aged in ammonia have a hysteresis loop type
H3 without an adsorption limit at p/p
0
close to 1. Hyster-
esis loops also shift toward larger relative pressures with
increasing NH
3
concentration. Similarly to xerogels, the
adsorbed volume of N
2
at p/p
0
< 0.2 is larger for the sam-
ple aged in ethanol, and decreases with ammonia concen-
tration (inset Fig. 4b).
Fig. 5 presents CO
2
adsorption isotherms for xero- and
aerogels obtained at 273 K and a relative pressure less than
0.03. Because the p/p
0
interval was small, adsorption of
CO
2
took place in ultramicropores (B< 0.7 nm) and on
the supermicropore walls [19]. Xerogels aged in ethanol
adsorbed between two and four times more CO
2
than those
aged in ammonia, indicating a larger micropore volume
when aging in ethanol. Aerogels hardly adsorbed CO
2
,
denoting lack of microporosity in samples dried under
supercritical condition for ethanol.
From adsorption data from N
2
at 77 K and CO
2
at
273 K, it is possible to obtain textural parameters to carry
out a quantitative comparison of aging and drying. Table 2
includes specic surface areas determined by the BET
method. BET surface areas (a
BET
) are in the range of
525697 m
2
g
1
for xerogels and between 337 and
549 m
2
g
1
for aerogels. Drying under supercritical condi-
tions results in smaller surface areas. Table 2 also shows
micropore volumes deduced by applying the Dubinin
Raduskevich (DR) method to the adsorption data of N
2
and CO
2
. Micropore volume deduced from N
2
adsorption
data is 0.263 cm
3
g
1
for the xerogel aged in ethanol and
drops to 0.170 cm
3
g
1
for xerogels aged in 2 M NH
3(aq)
.
For all samples, V
miN
2

is higher than V
miCO
2

, which can
be related to the pore size and adsorption conditions.
Because of the higher adsorption temperature and lower
relative pressure range, CO
2
only lls ultramicropores,
while N
2
also lls wider micropores [19]. Therefore, the lar-
ger amount of V
miN
2

compared to V
miCO
2

indicates a wide
distribution of micropore diameters. However, adsorption
of N
2
and CO
2
at very low relative pressures can also be
attributed to monolayer formation in mesopores, which
already occurs at relatively low pressures and is dependent
on both the mesopore size and the mesopore surface area
[20].
Mesopore volume (V
meso
) of xerogels was obtained by
the dierence between the amount adsorbed at the plateau,
which is a measure of the adsorption capacity, and micro-
pore volume obtained by the DubininRadushkevich
method. In the case of aerogels, mesopore volume was
deduced by the dierence between the amount adsorbed
at the upward swing and downward swing at the linear seg-
ment of the isotherms at relative pressures in the range of
0.30.7 [18] (Table 2). While xerogels aged in ethanol are
mainly microporous, with the micropore volume constitut-
ing 62% of the total pore volume (Fig. 6), aging alcogels in
NH
3(aq)
solution decreases the volume of micropores and
increases the mesopore contribution. For 0.5 M and 2 M
NH
3(aq)
solutions, mesopore volume is 65% and 73% of
total pore volume, respectively.
Fig. 7 shows the pore size distribution (PSD) obtained
from adsorption data using the BarretJoynerHalenda
(BJH) method [21] implemented in the software provided
with the ASAP 2010 adsorption apparatus. The peaks on
the distribution of xerogels aged in NH
3(aq)
are sharp.
0.0
0.5
1.0
1.5
2.0
2.5
0 0.01 0.02 0.03
p/p
0
n
a
/

m
m
o
l

g
-
1
XG-EtOH XG-0.5 M NH3 XG-2 M NH3
0.0
0.5
1.0
1.5
2.0
2.5
0 0.01 0.02 0.03
p/p
0
n
a
/

m
m
o
l

g
-
1
AE-EtOH AE-0.5 M NH3 AE-2 M NH3
b
a
Fig. 5. Adsorption isotherms of CO
2
at 273 K of (a) xerogels and (b)
aerogels aged in ethanol and NH
3(aq)
.
278 J. Estella et al. / Microporous and Mesoporous Materials 102 (2007) 274282
The maxima appear at 4.0 nm for the xerogel aged in 0.5 M
NH
3(aq)
and at 5.4 nm for the xerogel aged in 2 M ammo-
nia. Xerogels aged in EtOH show a broad pore size distri-
bution with the maximum overlapping the micropore size.
Table 2 also includes aerogel macropore volumes
(V
macro
) from mercury porosimetry and total pore volumes
obtained from two dierent methods; the sum of micro-,
meso- and macropore volumes (V
t
); and the inverse of bulk
and apparent densities from mercury and helium pycnom-
etries (V
t(q)
),
V
tq

1
q
Hg

1
q
He
2
Aerogels are macroporous materials, with macropore
volume constituting over 92% of the total pore volume,
which increases for alcogels aged in ammonia (Fig. 6).
Except for the xerogel aged in ethanol, the concordance
between the two methods used to obtain total pore volume
is higher than 85%, which is acceptable taking into account
the diversity of techniques and the dierences in the porous
texture of the samples. As for the xerogel aged in ethanol,
the total volume of pores obtained from the density calcu-
lation is approximately half the sum of micro-, meso- and
macropore volumes.
Under acidic conditions, weakly branched alcogels are
formed because the condensation rate is low [4]. The com-
pliant structure can freely shrink in response to solvent
removal. The enormous capillary pressure attained at the
nal stage of drying due to the tiny pores causes a further
compacting of the structure. The xerogel aged in ethanol
mainly has a microporous texture. However, aging alcogels
under NH
3
solution increases cross-linking between clus-
ters and the solubility of the skeletal phase, which allows
the structure to reorganize via dissolutionreprecipitation.
Condensation causes some modication of the pore struc-
ture in the wet gel, but its most remarkable eect is a
strengthening of the gel network that reduces the amount
of shrinkage which occurs during aging [22]. As the solvent
is removed, individual clusters undergo shrinkage and
Table 2
Textural parameters of xero- and aerogels aged in ethanol, 0.5 M NH
3
and 2.0 M NH
3
Aging a
BET
/m
2
g
1
Micropore volume (DR)/cm
3
g
1
V
meso
/cm
3
g
1
V
macro
/cm
3
g
1
Total pore volume/cm
3
g
1
V
miN2
V
miCO2
V
t
c
V
t(q)
d
Xerogels
EtOH 697 0.263 0.163 0.159
a
ND 0.422 0.160
0.5 M NH
3
683 0.218 0.108 0.407
a
ND 0.625 0.501
2.0 M NH
3
525 0.170 0.098 0.453
a
ND 0.623 0.618
Aerogels
EtOH 549 0.149 0.054 0.204
b
4.38 4.73 5.16
0.5 M NH
3
381 0.111 0.041 0.162
b
6.04 6.31 6.46
2.0 M NH
3
337 0.097 0.034 0.098
b
6.12 6.32 6.48
ND: non-detected.
a
Obtained by the dierence between the amount adsorbed at the plateau and DR micropore volume.
b
Deduced by the dierence between the amount of N
2
adsorbed in the relative pressure range 0.30.7.
c
Total pore volume obtained from aerogels by summing of V
miN2
, V
meso
and V
macro
.
d
Total pore volume from the dierence of inverse bulk and apparent densities from mercury and helium pycnometries.
0
20
40
60
80
100
X
G
-
E
t
O
H
X
G
-
0
.
5
M

N
H
3
X
G
-
2
M

N
H
3
A
E
-
E
t
O
H
A
E
-
0
.
5
M

N
H
3
A
E
-
2
M

N
H
3
p
o
r
o
s
i
t
y
/

%
micro meso macro
Fig. 6. Porosity distribution, expressed as volume percentage, of xero- and
aerogels aged in ethanol and aqueous ammonia.
0.0
0.4
0.8
1.2
1.6
0 25 50 75 100 125 150
Pore diameter /
d
V
/
d
l
o
g
(
D
)

P
o
r
e

v
o
l
u
m
e

/
c
m

g
-
1

-
1
XG-EtOH XG-0.5 M NH3 XG-2M NH3
Fig. 7. Pore size distribution obtained from adsorption data using the
BJH method.
J. Estella et al. / Microporous and Mesoporous Materials 102 (2007) 274282 279
rearrangement to achieve higher coordination number, but
shrinkage stops at an earlier stage of drying due to the sti-
ness of the impinging clusters. A high pore volume results
because the stier gel produced by aging does not shrink as
much under the inuence of capillary pressure [23]. When
drying under supercritical conditions, the solvent is
removed without stress on the pores. Therefore, the
original structure of the solvated gel is less aected than
when drying alcogels under atmospheric conditions, where
capillary stress produces shrinking and reduces pore
diameter.
3.4. Scanning and transmission electron microscopy
Fig. 8ac shows the particle morphology of xerogels
obtained by SEM. The xerogel aged in ethanol has a highly
dense surface morphology, where macropores are not
observed. In no case could micropores be seen due to the
limits of SEM resolution. Xerogels aged in ammonia show
aggregates of particles with diameters around 200 nm.
Between the aggregates, pores stand out with diameters
in the range of 2040 nm. As the ammonia concentration
in the aging media is increased from 0.5 to 2.0 M, aggre-
gates become larger and more compact, but SEM did not
show major dierences in the mesopore sizes. Aerogel
micrographs (Fig. 8df) are similar independent of the
aging media. Enlargement of the pictures shows that the
clusters are made up of spherical particles in the range of
50100 nm with macropores between particles.
As an example, Fig. 9 shows high resolution TEM
micrographs of (a) a xerogel aged in ethanol, (b) a xerogel
aged in 2 M NH
3(aq)
, and (c) an aerogel aged in ethanol.
The three samples appear amorphous and the detail from
micrographs agrees with textural parameters obtained by
gas adsorption, Hg porosimetry and density measurements.
The xerogel aged in ethanol shows a dense network in
which micropores can hardly be resolved. The xerogel aged
in 2 M NH
3(aq)
is less dense than the xerogel aged in etha-
nol, and porosity within a cluster is made up of relatively
uniform small mesopores. The aerogel network has a very
low density macroporous network with a wide pore size
distribution.
Fig. 8. SEM micrographs of xerogels aged in (a) ethanol, (b) 0.5 M NH
3(aq)
and (c) 2.0 M NH
3(aq)
, and aerogels aged in (d) ethanol, (e) 0.5 M NH
3(aq)
and
(f) 2.0 M NH
3(aq)
.
280 J. Estella et al. / Microporous and Mesoporous Materials 102 (2007) 274282
4. Conclusions
Aging and drying conditions strongly aected the por-
ous texture of silica gels. The surface area and micropore
volume was higher in xerogels than in aerogels. Xerogel
aged in ethanol was mainly microporous, while xerogels
aged in ammonia were mesoporous. Increasing the ammo-
nia concentration in the aging solution resulted in a larger
volume and diameter of mesopores. The maxima from the
BJH distribution appeared at 4.0 nm for the xerogel aged
in 0.5 M NH
3(aq)
, and at 5.4 nm for the xerogel aged in
2 M NH
3(aq)
. Aerogels contained over twice the pore
volume of xerogels, and were macroporous materials. Mac-
ropore volume constituted over 92% of the total pore vol-
ume, independent of the aging media.
The skeletal density of aerogels was larger than that of
xerogels, and samples aged in NH
3(aq)
had a larger density
than samples aged in ethanol. Esterication reactions
inside the reactor promote cross-linking by condensation
between clusters, which results in a higher skeletal density
and an increase in the absorbance of SiO related IR
bands. Cross-linking strengthens the gel network and
reduces the amount of shrinkage under atmospheric condi-
tions. In aerogels, the original structure of the solvated gel
is less aected than in xerogels because the solvent is
removed without stress on pores.
SEM and TEM micrographs conrm the textural prop-
erties of xero- and aerogels deduced by gas adsorption, Hg
porosimetry and density measurements.
Acknowledgments
This work was supported by Ministerio de Ciencia y
Tecnolog a (BQU2002-04090-CO2-02 and CTQ2005-
08099-CO3-02-BQU). Juncal Estella Red n is thankful to
Departamento de Industria y Tecnolog a, Comercio y Tra-
bajo del Gobierno de Navarra for the fellowship. The
authors are grateful to two anonymous reviewers for their
fruitful comments.
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