Fractal Studies on Titanium-Silica Aerogels using SMARTer

Edy Giri Rachman Putra1, Abarrul Ikram1, Bharoto1, Eddy Santoso1,

Tan Chiar Fang2, Noorddin Ibrahim2, Abdul Aziz Mohamed3
1
Neutron Scattering Laboratory
Center of Technology for Nuclear Industrial Materials
National Nuclear Energy Agency of Indonesia (BATAN)
Kawasan Puspiptek Serpong, Tangerang 15314, Indonesia
2
Department of Physics, Faculty of Science
Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor, Malaysia
3
Materials Technology Group, Industrial Technology Division,
Agensi Nuklear Malaysia, 43000 Kajang, Selangor, Malaysia

ABSTRACT

Power-law scattering approximation has been employed to reveal the fractal structures of solid-state titanium-silica
aerogel samples. All small-angle neutron scattering (SANS) measurements were performed using 36 meters SANS
BATAN spectrometer (SMARTer) at the neutron scattering laboratory (NSL) in Serpong, Indonesia. The mass fractal
dimension of titanium-silica aerogels at low scattering vector q range increases from –1.4 to –1.92 with the decrease of
acid concentrations during sol-gel process. These results are attributed to the titanium-silica aerogels that are growing to
more polymeric and branched structures. At high scattering vector q range the Porod slope of –3.9 significantly down to
–2.24 as the roughness of particle surfaces becomes higher. The cross over between these two regimes decreases from 0.4
to 0.16 nm-1 with the increase of acid concentrations indicating also that the titanium-silica aerogels are growing.

Keywords: SANS, aerogels, fractals, power-law scattering

Corresponding address: e.giri@centrin.net.id

INTRODUCTION rocks9 and gels7,10. The theoretical and experimental

Aerogel is one of the most interesting solid
materials that has very wide-range applications, recently.
Because of its low density and large specific surface area,
aerogels have been applied for absorber of dust1, a host
matrix for long life nuclear waste2 or a carrier for active
compound or pharmaceuticals in drug-delivery system3.
A spesific application of aerogles based on their optical
properties is for Cherenkov radiation detectors4 and
optical sensors. However, the most recent application of
aerogles is for catalysts5.
Unlike conventional foam, aerogel is a special
porous materials with extreme porosity in a nano-to-
micrometer scale. It is composed of individual particles
with a few nanometer in size which are linked in three
dimensional structure. Aerogels are typically prepared
by synthesizing metal-alkali precursors in an excess
solvent by sol-gel process compared to traditional glass
melting or ceramics powder methods. The solvent is
removed from the pores under supercritical conditions,
thereby the large capillarity force and shrinkage that
always occur when liquid is removed from small pores
will be avoided.
Porous materials which behaves as disordered solid
materials has to be characterized to obtain its structure
information such as pore dimension, surface structures,
etc. Fractal concept has been found6 to be important in
many structure studies of disordered materials since
many processes as well as the structures can be
described and understood in terms of non-integral
dimensions.
Small-angle scatterings of neutron (SANS) and X-
ray (SAXS) have proved to be well suited and direct
techniques to investigate the microsructure of fractals
and other disordered systems on nanometer scale, such
as polymers7,8, biological molecules, aggregates7, mineral
small-angle scattering techniques have been developed
and well established11. A characteristic feature of the
small-angle scattering from fractal scatterers and many
other disorder solids is often obeys a “power-law”
scattering in the magnitude of the scattering vector q
given as
I ( q ) ∝ q −D (1)
where D related to the structure of the scatterer is
positive constant. Eq. (1) applies only in the regime ξ
>> q-1 >> a, where a is a typical chemical or bond
distance related to local structure and ξ is the
correlation length or average diameter of a scatter.
In discussion of small-angle scattering from
fractals, there are two types of fractal systems, i.e. mass
fractals and surface fractals. Mass fractals are aggregates
of primary particles and the distribution of mass M(r)
within a sphere of radius r is given by
M (r ) ∝ r DM (2)
where DM is the mass fractal dimension and has a non-
integer value for random or disorder object, 1 ≤ DM ≤ 3.
However, for rods, disks, and spheres, DM respectively is
1, 2, and 3. In contrast to mass fractals, for surface
fractals the object is uniform, so that no scattering
occurs from the bulk. In this case the magnitude of
scattering vector is given by
I ( q ) ∝ q Ds −6 (3)
where Ds is the three-dimensional surface fractal
dimension which relates surface area, A, to length. If the
surface is within a sphere of radius r, then
S (r ) ∝ r 2−Ds (4)
The meaningful values of Ds lie in the interval 2 ≤ Ds ≤
3. When a surface is smooth rather than fractal or non-

1
fractal, Ds = 2 and scattering intensity I(q) decays as q-4
in Eq. (3) as the surface becomes independent of r. This
behaviour is commonly called Porod’s law. For fractal
surface, Porod slopes between -3 and –4 are expected. At
large scattering vector q, the intensity I (q) for scattering
from a thin disk has slope of –2 and –1 from a thin rod,
Eq. (1).
In this paper, we report the fractal structure change of
titanium-silica aerogels prepared by sol-gel process
method with various acid concentrations and then
analyzed the small-angle neutron scattering data as a
direct technique to determine the fractal dimension.
EXPERIMENT
The titanium-silica aerogels with various acid
concentrations from 1 N to 1.75 N were synthesized with
sol-gel process method at Universiti Teknologi Malaysia,
Malaysia[12]. The sample then was poured into 1 mm
thick quartz cell and then covered with other 1 mm thick
quartz cell as a sandwich with sample thickness of 1 mm.
The SANS experiments were performed using the 36
meter SANS-BATAN spectrometer (SMARTer) at the
neutron scattering laboratory (NSL) – BATAN in
Serpong, Indonesia. The rotational speed of the
mechanical velocity selector was adjusted to 5000 rpm
with tilting angle of 0° to generate neutron wavelength of
0.39 nm with the spread of 0.135. Three different
sample-to-detector distances of 1.5, 4 and 13 m have
been set up covering the scattering vector Q-range of
0.03 < q (nm-1) < 3. The length of collimation or sample-
to-source distance was set for 4 and 8 m. The exposure
time for each aerogel sample and each sample-to-
detector distance was 2 hours. The scattering data were
corrected for empty cell as a background, electronic
background as a noise, sample transmission and detector
efficiency using the SMARTer data reduction software.
For data correction, empty cell, electronic background,
and incoherent scatterings from water were collected for
10, 12 and 10 hours, respectively. During the experiment,
the temperature was maintained at room temperature.
RESULTS AND DISCUSSION
Figure 1 shows a typical power-law scattering profiles
from silica aerogles which have two power-law regimes13.
At high q range or short-length, scattering from smooth
particles results in a slope of –4, while at intermediate q
range the scattering slope is –1.93, representing a thin
disk shape, describing the particle aggregation in a
polymeric structure by a mass-fractal morphology close
to D ~ 2. It is consistent with Eqs. (1) and (3), with D = 2
and Ds = 2, respectively. However, at low q-range the
curve does not show the independent scattering on
scattering vector q since the dimension of particle is
larger than ξ and it is in uniform structure13.
4
10
3
10
Figure 1 SANS profiles from pure silica aerogels were
obtained in the wide scattering vector q-range.
Figure 2 shows the power-law scattering profiles from
silica aerogels containing titanium as a function of acid
concentrations. A similar scattering profile with silica
aerogles is shown from titanium-silica aerogel sample at
the lowest acid concentration of 1 N, Figure 2a. The

2
change of slopes at high and intermediate q range is

10
related to changing of particle structures as the effect of
Intensity

4 4
10 10 1
10 -1.4
(a)
3 (b)
3
10 10 0
4 4
10 10
10
2 2
10 10-1
ensity

ensity

3 3
10
(c) (d)

10 10
Figure 2 SANS profiles from titanium-silica aerogels with various acid concentrations during sol-gel process (a) 1 N ;
(b) 1.25 N ; (c) 1.5 N and (d) 1.75 N. The slopes were determined by least square fitting

10
1 1
10-2 2 -1.
2 2
the acid concentration. The particles become rougher on REFERENCES
the surface as the slope decreases from -3.97 to -3.93,
while the aggregate has more elongated shape as the
magnitute of scattering intensity I(q) = q-1.5 compare to
that of the silica aerogels, I (q) = q-1.93.

Figure 2 also shows the slopes of titanium-silica aerogles

with acid concentrations of 1 N (Figure 2a) to 1.25 N
(Figure 2b) at high q-range that changed dramatically
from –3.9 to –2.35. This indicates that increasing the
acid concentration 0f 0.25 N from 1 N has altered the
surface structure from relatively smooth particles to
highly rough particles or relatively dense polymeric
structure13 and the surface fractals is vanished.
Meanwhile, by further increasing the acid
concentrations, the slope does not change as much as the
first one. It is also pointed out that the slopes at
intermediate q-range show another fashion where they
decrease from –1.42 to –1.92 gradually when the acid
concentration increases from 1 N to 1.75 N, Figure 2a-d.
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aerogels are growing to more polymeric and branched
structures with the magnitute scattering intensity I(q) =
q-2 by increasing the acid concentration.

The cross over between two regimes for the titanium-

silica aerogels at various concentratiosn can be related to
the size of an agglomeration of particles in the aerogels
with the order of 2π /q0 as in the Bragg relation. As the
acid concentration increases from 1 N to 1.75 N, a
breaking point which roughly marks the change of slope
in the curve decreases from 0.4 nm-1 to 0.16 nm-1 which
corresponds to particle size of 17.7 nm to 39.3 nm. These
results also indicate that the titanium-silica aerogels are
growing with the increase of acid concentration. Similar
to the fractal structures, the mass fractal structure was
indentified in the tintanium-silica aerogels and changed
by increasing the acid concentration.

CONCLUSION
An excellent performance in revealing the fractal
structures of titanium-silica aerogels has been
accomplished by SANS BATAN spectrometer
(SMARTer). Power-law scattering on titanium-silica
aerogels at high and intermediate q-range changes as a
function of acid concentrations. The acid concentration
affected the changing of fractal structure of aerogels
more rather than the impurities in titanium. Mass fractal
structures have been found with the dimension DM
between 1.42 and 1.92.

3
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