Applied Surface Science 252 (2006) 4289–4297

www.elsevier.com/locate/apsusc

Surface chemical modification of TEOS based silica aerogels

synthesized by two step (acid–base) sol–gel process
Sharad D. Bhagat, A. Venkateswara Rao *
Air Glass Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004, Maharashtra, India
Received 8 March 2005; received in revised form 7 July 2005; accepted 7 July 2005
Available online 22 August 2005

Abstract

The present paper describes the comparative studies on the hydrophobic and physical properties of the tetraethoxysilane
(TEOS) based silica aerogels prepared by two step sol–gel process followed by supercritical drying. Silica alcogels were
prepared by keeping the molar ratio of TEOS:methanol (MeOH):H2O (acidic):H2O (basic) constant at 1:33:3.5:3.5 with oxalic
acid and ammonium hydroxide concentrations fixed at 0.001 and 1 M, respectively. In all, nine different co-precursors (CP) of
the type RnSiX4
n, have been used. The aerogels have been characterized by density, porosity, percentage of volume shrinkage,
optical transmission, contact angle and thermal conductivity measurements. The surface chemical modification of silica
aerogels was confirmed by the presence of C–H and Si–C peaks at 2900, 1450 and 840 cm
1, respectively, from the Fourier
transform-infrared spectroscopy (FT-IR). The microstructure of the aerogels was studied using transmission electron micro-
scopy (TEM) and scanning electron microscopy (SEM) techniques. In addition to these studies, the stability of the hydrophobic
aerogels against an organic impurity (methanol, in the present studies) in water has also been studied.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Silica aerogels; Hydrophobicity; Thermal stability; SEM; TEM

1. Introduction 750 nm in the visible region) and low bulk density

(0.05 g/cm3) [1–3]. Therefore, the aerogels have
Silica aerogels are usually derived by the sol–gel been used in a variety of applications, such as super
process followed by supercritical drying. They have thermal insulation in solar window systems, refrig-
open cell structures yielding nanostructured materials erators, thermos flasks [4,5], inertial confinement
with extremely high surface area (1000 m2/g). These fusion (ICF) targets for thermonuclear fusion reac-
features lead to the unique properties, such as high tions [6], Cerenkov radiation detector media in high
porosity (95%), high optical transmission (90% at energy physics [7,8], hydrophobic aerogels for oil
absorption and organic solvent absorption from water
* Corresponding author. Tel.: +91 2312690571;
[9].
fax: +91 2312657262. However, the typical aerogels readily become wet
E-mail address: avrao_phy@unishivaji.ac.in (A.V. Rao). by most of the liquids resulting in collapse of the

0169-4332/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2005.07.006
4290 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297

aerogel network. Also, when the aerogels are exposed 2. Experimental procedures
to the ambient atmosphere, they absorb moisture from
the humid surroundings resulting in deterioration of 2.1. Sample preparation
the aerogel network due to the breaking of Si–O–Si
bonds by the nucleophilic attack on Si atom by OH
A novel two step (acid–base) catalyzed sol–gel
ions present in the humid surroundings. The surface of process was used to prepare the silica alcosols and
the aerogel can be modified so as to repel the water and alcogels because it offers an excellent control over the
to some extent aqueous solutions as well. The property rates of hydrolysis and condensation reactions by the
of the materials that inhibits wetting by liquid water is use of proper amounts of acid and base catalysts,
called as hydrophobicity. The hydrophobicity is very during the reactions. The process involves the
essential for the long term use of the silica aerogels in following two steps:
various applications. In order to have such a
hydrophobic property in the material, the solid–liquid (i) Tetraethoxysilane (TEOS) was first diluted in
interfacial energy should be greater than that of the methanol and it was hydrolyzed with a partial
solid–vapour interfacial energy, as given by the amount of water under the acidic conditions
Young’s equation [10]: (oxalic acid).
(ii) Condensation of these hydrolyzed species (i.e. Si–
g sv ¼ g sl þ g lv cos u (1) OH) was carried out in the presence of a base
catalyst, such as ammonium hydroxide (NH4OH).
where gsv, gsl and glv are solid–vapour, solid–liquid
and liquid–vapour interfacial energies, respectively, In order to compare the physical and hydrophobic
and u is the contact angle. properties of the aerogels, the co-precursor (CP)/
In the case of the aerogels, this condition can be TEOS molar ratio was varied from 0.3 to 1 by keeping
achieved by replacing H from the surface –OH groups the molar ratio of TEOS:MeOH:acidic H2O:basic H2O
by hyrdolytically stable Si-alkyl, Si-aryl or Si-phenyl constant at 1:33:3.5:3.5 along with the oxalic acid and
groups resulting in high-energy solid–liquid interface. NH4OH concentrations at 0.001 and 1 M, respectively.
There are several reports on the production of The time interval (T) before the base catalyst addition
hydrophobic aerogels using tetramethoxysilane was fixed at 24 h. In the present work, nine different
(TMOS) precursor, but the TMOS is five times organosilane compounds were used as the hydro-
costlier than the TEOS precursor and also toxic, which phobic reagents and they are: methyltrimethoxysilane
can cause blindness [11,12]. Therefore, the present (MTMS), dimethyldiethoxysilane (DMDS), trimethy-
work describes the use of two step (acid–base lethoxysilane (TMES), ethyltriethoxysilane (ETES),
catalyzed) sol–gel process for the production of propyltrimethoxysilane (PrTMS), phenyltriethoxysi-
hydrophobic silica aerogels using low cost and lane (PTES), phenyltrimethoxysilane (PTMS), vinyl-
environmental friendly metal alkoxide precursor and trimethoxysilane (VTMS) and vinyltriethoxysilane
a low cost solvent, such as tetraethoxysilane (TEOS) (VTES). All the chemicals used were of ‘purum’ grade
and methanol, respectively. In order to compare the from Fluka Company, Switzerland. Deionized water
physical and hydrophobic properties, nine different was used for the preparation of 0.001 M oxalic acid
co-precursors containing organic groups, such as and 1M NH4OH solutions. After stirring for about
alkyl, aryl and vinyl, have been used. 15 min, the resulting homogeneous sol was transferred
The surface chemical modification using phenyl- to the test tubes of 15 mm outer diameter and 150 mm
triethoxysilane (PTES) resulted in transparent height and subjected to gelation at room temperature
(80%) and hydrophobic aerogels (u = 1408) with (27 8C). The gelation time is the duration after the
the highest thermal stability, among all the co- preparation of sol, in which it seizes to move even
precursors, up to a temperature of 520 8C. Whereas, when the test tube is tilted or inverted [13]. After
the trimethylethoxysilane (TMES) modified aerogels gelation, the alcogels were aged for 2 days and then
showed negligible volume shrinkage with u as high dried supercritically separately for each co-precursor,
as 1488. in order to avoid the influence of the pore fluid of one
 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297 4291

gel on the other. The details of the supercritical drying angle meter (Tantec Company, USA). Good agree-
are given in our earlier publication [14]. ment has been observed by both the methods in the
The aerogels have been characterized by density, measurement of u.
porosity, percentage of volume shrinkage, optical The thermal stability of the hydrophobic aerogels
transmission, contact angle and thermal conductivity was tested by heating them in a furnace at various
measurements. The surface chemical modification temperatures. Here, the term thermal stability refers to
was confirmed using the FT-IR spectroscopy (Perkin- the temperature up to which the aerogel retains its
Elmer instruments, spectrum one, made in USA). The hydrophobic property and above which it becomes
microstructure of the aerogels was studied using hydrophilic. The thermal conductivity of the hydro-
transmissionelectronmicroscopy(TEM,Philips,Tecnai phobic aerogels was measured with C-T meter
F20 model) and scanning electron microscopy (SEM, (Teleph, France) by sandwiching a ring probe (a
model: JEOL, JSM-5600LV analyser) techniques. flexible printed circuit of thickness 0.2 mm and
dimension 60 mm  90 mm) in between two plane
2.2. Methods of characterization sheets of the aerogel sample.

The bulk density of the aerogel sample was

calculated by measuring its mass to volume ratio. 3. Results and discussion
The percentage of porosity of the aerogels was
calculated using the formula: When the alkoxides are hydrolyzed in the alcohols
  containing different alkyl groups, transesterification
r occurs as Brinker et al. found when the TEOS was
P ð%Þ ¼ 1
b  100 (2)
rs hydrolyzed in n-propanol [16]. In the present studies,
the hydrolysis of the TEOS precursor was carried out
where rb is the bulk density and rs is the skeletal
in methanol solvent resulting in transesterification as
density of the silica aerogels which was measured
per the following chemical reaction:
using helium pycnometry and its value was found to be
1900 kg/m3. The percentage of volume shrinkage (Vs, SiðOC2 H5 Þ4 þ CH3 OH
%) was determined from the change in the volumes of
$ SiðOC2 H5 Þ3 OCH3 þ C2 H5 OH (5)
the alcogel and the aerogel using the formula:
  With the use of methanol solvent and two step sol–gel
V
VS ð%Þ ¼ 1
1  100 (3) process, it was possible to obtain aerogels with better
V
hydrophobic and physical properties compared to the
where V is the volume of the aerogel and V1 is the earlier reports [17]. This is because of the smaller
volume of the alcogel. chain alkyl groups (–CH3) present in the methanol
The optical transmission of the aerogels (sample solvent, minimizing steric hindrance during hydroly-
thickness of 1 cm) was measured at a wavelength of sis, compared to the other solvents, such as ethanol,
750 nm using a spectrophotometer (Systronic 119, propanol, butanol, etc. [18]. The hydrophobic aerogels
USA). have been obtained, using nine different organosilane
To quantify the degree of hydrophobicity, the compounds, by co-precursor method poineered by
contact angle (u) of water droplet placed on the Schwertfeger et al. [19]. When sufficient amount of
hydrophobic aerogel, was calculated using the TEOS gets hydrolyzed, the silyl groups present in the
formula [15]: co-precursors get attached to the silica clusters as per
the following chemical reaction:
u 2h
tan ¼ (4)
2 W
where the base contact length W and height h of the ð6Þ
droplet were measured using a travelling microscope.
Also, the contact angle (u) was measured by contact where R is alkyl, aryl, phenyl or vinyl group.
4292 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297

It has been observed that the resulting aerogels show show the SEM images of the PTES modified aerogels
significant variation in their physical and hydrophobic prepared with PTES/TEOS molar ratios of 0.3 and 1,
properties depending on the type of co-precursor used respectively. Out of all the nine co-precursors,
for the surface chemical modification. aerogels prepared with MTMS, DMDS and PTES
co-precursors show maximum optical transmission
3.1. Gelation time and optical transmission (80%) for the molar ratio of CP/TEOS = 0.3.

It has been observed that as the molar ratio of co- 3.2. Bulk density, volume shrinkage and thermal
precursor (CP)/TEOS increased from 0.3 to 1, the conductivity
gelation time increased for all the co-precursors as can
be seen from the Table 1. This is due to the fact that the The bulk density and volume shrinkage of the
rates of hydrolysis and condensation reactions are aerogels increased with increase in CP/TEOS molar
retarded by the non-hydrolyzable alkyl groups present ratio from 0.3 to 1 for all the co-precursors except the
in the co-precursors. Further, it has also been observed aerogels modified with TMES and PTES co-precursors.
that as the chain of alkyl group increases (from methyl For the aerogels modified with TMES and PTES co-
to propyl group), the gelation time increased from 2 to precursors, the bulk density was found to decrease from
14 h due to the increased steric hindrance. 0.207 to 0.036 and 0.113 to 0.036 g/cm3, respectively,
The optical transmission of the aerogels was found and the percentage of volume shrinkage was found to
to decrease (from 80 to 2% for PTES co-precursor) decrease from 38 to 5% and 42 to 16%, respectively, as
with an increase in the CP/TEOS molar ratio from 0.3 the CP/TEOS molar ratio increased from 0.3 to 1. This
to 1. This is due to the growth of larger and irregular is due to the fact that the presence of more organic
particles and pore sizes with an increase in CP/TEOS groups in the TMES and PTES co-precursors increases
molar ratio. This is seen from the Fig. 1a and b, which the elasticity of the aerogel network resulting in

Table 1
Physical properties of the TEOS aerogels modified using various co-precursors
Co-precursor Molar ratio Gelation Bulk density, Porosity, Transparency, Volume
(CP/TEOS) time (Tg) rb (g/cm3) (0.005) P (%) T (%) @750 nm (2%) shrinkage, Vs (%) (3%)
MTMS 0.3 1h 0.091 95 76 30
1.0 2h 0.132 94 60 34
ETES 0.3 3h 0.094 95 68 35
1.0 10 h 0.117 93 4 25
PrTMS 0.3 4h 0.049 97 46 26
1.0 14 h 0.163 91 1.0 37
DMDS 0.3 3h 0.095 94 80 40
1.0 2 days – – – –
TMES 0.3 5h 0.207 89 74 38
1.0 8h 0.036 98 3 5
PTMS 0.3 2h 0.137 92 43 47
1.0 No gelation – – – –
PTES 0.3 1h 0.113 94 80 42
1.0 4h 0.036 98 2 16
VTMS 0.3 45 min – – – –
1.0 2h 0.140 92 20 31
VTES 0.3 1 h 10 min 0.075 96 66 25
1.0 2 h 30 min 0.122 93 2 24
 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297 4293

Fig. 1. Scanning electron micrographs of TEOS based aerogels

modified with PTES co-precursor: (a) molar ratio of PTES/ Fig. 2. Transmission electron micrographs of TEOS based aerogels
TEOS = 0.3 and (b) molar ratio of PTES/TEOS = 1. modified with TMES co-precursor: (a) molar ratio of TMES/
TEOS = 0.3 and (b) molar ratio of TMES/TEOS = 1.

lowering of the volume shrinkage during drying and

hence decrease in the bulk density. Similar results have The thermal conductivity of the aerogels was
been obtained by Karmer et al. for various poly- found to be strongly dependant on the bulk density as
methyldisiloxane/TEOS systems [20]. The negligible seen from the Table 1. It has been observed that as
volume shrinkage (2%) of the TMES modified the bulk density decreased from 0.163 g/cm3 (for
aerogels can also be due to the ’spring back effect’ PrTMS) to 0.036 g/cm3 (for TMES), the thermal
[21]. Fig. 2a and b show the TEM images of the TMES conductivity decreased form 0.085 to 0.042 W/m K,
modified aerogels prepared with TMES/TEOS molar respectively. This is due to the fact that major heat
ratios at 0.3 and 1, respectively. From the TEM images, transfer through the aerogels takes place via solid
it is clearly seen that the aerogel network is denser for thermal conduction which is directly proportional to
TMES/TEOS = 0.3 than that of 1. the bulk density [22].
4294 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297

resulting in better hydrophobicity. This has been

confirmed by the FT-IR spectra (for VTES modified
aerogels) shown in Fig. 4a and b. It is seen from the
Fig. 4a and b that as the VTES/TEOS molar ratio
increases from 0.6 to 1, the peak intensities of C–H (at
2900 and 1450 cm
1) and Si–C (at 840 cm
1)
increase clearly indicating an increase in the number
of alkyl/aryl groups in the silica aerogel network and
hence resulting in better hydrophobicity. The same has
been observed for all other co-precursors. Also it has
been observed that as we go from methyl (MTMS) to
propyl (PrTMS) groups, the C–H content increases
resulting in enhanced hydrophobic properties. This
increase in C–H peak at 2900 and 1450 cm
1 is clearly
seen from the Fig. 5a–c. The contact angle (u)
increased from 1388 to 1468 for the methyl to propyl
surface modification. The TMES modified aerogels
showed the highest hydrophobicity (among all the co-
precursors used) with the contact angle (u) as high as
1488.
The thermal stability of the hydrophobic aerogels
was tested by heating them in a furnace at various
temperatures from 100 to 550 8C and from time to time
testing with water. It has been observed that the aerogels
modified with VTMS and VTES co-precursors show
the lowest thermal stability up to a temperature of
200 8C and above which aerogels absorb water readily.
Whereas, the PTMS and PTES modified aerogels
showed the highest thermal stability of 500 and 520 8C,
respectively. The ETES, PrTMS, DMDS and TMES
Fig. 3. Photographs showing the water droplets on the hydrophobic
modified aerogels are thermally stable upto the
aerogels prepared with: (a) PTES/TEOS = 0.3 and (b) PTES/
TEOS = 1. temperatures of 240, 250, 420 and 270 8C, respectively.

3.3. Hydrophobicity and thermal stability 3.4. Stability of hydrophobic aerogels against an
organic impurity
The degree of hydrophobicity was quantified by
measuring the contact angle (u) of a water droplet In order to study the stability of the hydrophobic
placed on the hydrophobic aerogel surface. Fig. 3a and aerogels against an organic impurity (i.e. for example,
b show the photographs of water droplets placed on the methanol in the present studies), homogeneous solu-
hydrophobic aerogels prepared with PTES/TEOS tions of deionized water containing various percentages
molar ratios of 0.3 and 1, respectively and the of methanol were prepared. These solutions were
corresponding contact angles are 1408 and 1468, further used to study the contact angle measurements
respectively. The contact angle measurements showed (u) with various hydrophobic aerogels prepared with the
that u increases with increase in CP/TEOS molar ratio molar ratio of CP/TEOS = 1. Table 3 shows the contact
from 0.3 to 1, as shown in the Table 2. This is due to angle values, as a function of percentage of methanol in
the fact that an increase in the CP/TEOS molar ratio water, for various co-precursors.
results in the replacement of more and more number of It is clearly seen from the Table 3 that even though
H from OH groups by Si-alkyl/aryl/vinyl groups the PTES modified aerogels show the highest thermal
 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297 4295

Table 2
Hydrophobic properties of the TEOS aerogels modified using various co-precursors
Co-precursor Molar ratio Thermal conductivity Thermal stability Contact angle,
(CP/TEOS) (W/m K) (5%) (8C) (5 8C) u (8) (28)
MTMS 0.3 – – 136
1.0 0.08 240 146
ETES 0.3 – – 138
1.0 0.073 240 146
PrTMS 0.3 – – 136
1.0 0.085 250 146
DMDS 0.3 – – 138
1.0 – 420 Cracked sample
TMES 0.3 – – 140
1.0 0.042 270 148
PTMS 0.3 – – Cracked sample
1.0 – 500 Cracked sample
PTES 0.3 – – 140
1.0 0.044 520 146
VTMS 0.3 – – Cracked sample
1.0 0.086 200 –
VTES 0.3 – – 134
1.0 0.072 200 140

Fig. 4. FT-IR spectra of the hydrophobic aerogels prepared with Fig. 5. FT-IR spectra of the hydrophobic aerogels prepared with
VTES co-precursor for: (a) molar ratio of VTES/TEOS = 0.6 and (b) different co-precursors for the molar ratio of CP/TEOS = 1: (a)
molar ratio of VTES/TEOS = 1. MTMS, (b) ETES and (c) PrTMS.
4296 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297

Table 3
The contact angle measurements as a function of methanol percentage in water for various co-precursors, where CP/TEOS = 1
Co-precursor Contact angle u (8) for various methanol percentages in water
20% 40% 60%
MTMS 134 123 Absorption of the liquid drop
ETES 142 124 Absorption of the liquid drop
TMES 140 112 Absorption of the liquid drop
PrTMS 144 133 Absorption of the liquid drop
PTES 137 Absorption of the liquid drop Absorption of the liquid drop
VTES 134 Absorption of the liquid drop Absorption of the liquid drop

stability of 520 8C, they are less stable against the contact angle (u) found to be increased from 1388 to
methanol (i.e. they readily absorb the water droplet 1468. Use of the TMES co-precursor yielded aerogels
containing more than 20% methanol) compared to the with negligible volume shrinkage (2%) and hence
alkyl (MTMS, ETES, TMES and PrTMS) modified they have very low density (0.036 g/cm3), low thermal
aerogels which are stable for water containing 40% conductivity (0.042 W/m K) and with contact angle (u)
methanol. The contact angle (u) decreases (from 1468 as high as 1488 (highest hydrophobicity among all the
to 1338 for PrTMS) with an increase in methanol co-precursors used in the present studies) for the molar
percentage (from 0 to 40%) in water. This is due to the ratio of TMES/TEOS = 1, but the aerogels are opaque.
fact that the surface tension of water decreases with an The surface chemical modification with PTMS co-
increase in methanol percentage leading to the precursor resulted in higher thermal stability but the
lowering of solid–liquid interfacial energy, i.e. gsl as aerogels are cracked. The aerogels modified with
given in the Eq. (1). This decrease in the solid–liquid VTMS and VTES co-precursors show lowest thermal
interfacial energy is measured in terms of the contact stability of 200 8C. The PTES and VTES modified
angle (u) as it is directly proportional to the surface aerogels show less stability against methanol absorp-
tension of the liquid. Above a certain percentage of tion compared to the MTMS, ETES, TMES and PrTMS
methanol in water, the surface tension of the liquid modified aerogels, which are stable for the water drop
becomes so less that it gets readily absorbed through containing 40% methanol. Monolithic, transparent
the solid–liquid interface [23]. This limit of the (80%) and hydrophobic (u = 1408) aerogels with the
absorption of the percentage of methanol in water highest thermal stability up to a temperature of 520 8C
depends on the chemical groups present on the solid have been obtained for the molar ratio of PTES/
surface as well. That is why both phenyl and vinyl TEOS = 1.
modified aerogels show absorption of methanol
greater than 20% in water, whereas MTMS, ETES,
TMES and PrTMS modified aerogels show stability Acknowledgements
against the water containing 40% of methanol.
The authors are grateful to the Department of
Science and Technology (DST), New Delhi, for the
4. Conclusions financial support for the research project on ‘‘Aero-
gels’’ (No. SR/S2/CMP-01/2002). The authors are
Hydrophobic silica aerogels, based on the low cost highly thankful to Dr. Hiroshi Hirashima, Faculty of
precursor, such as TEOS and low-cost methanol Science and Technology, Keio University, Japan for
solvent, were prepared, using various alkyl, aryl and his help in the transmission electron microscopy
vinyl alkoxysilane compounds, by two step sol–gel (TEM) studies and Prof. T.N. Guru Row, Dr. K.R.
process. As the chain of alkyl groups present in the co- Kannan and Mr. Satyanarayana, Solid State and
precursor, increased from methyl to ethyl to propyl (i.e. Structural Chemistry Unit, Indian Institute of Science,
for MTMS, ETES, PrTMS co-precursors, respectively), Bangalore, India, for their help in the SEM studies.
 S.D. Bhagat, A.V. Rao / Applied Surface Science 252 (2006) 4289–4297 4297

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