J.

of Supercritical Fluids 166 (2020) 104997

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Novel approach of silica-PVA hybrid aerogel synthesis by

simultaneous sol-gel process and phase separation
Bartosz Babiarczuk a,∗ , Daniel Lewandowski a , Anna Szczurek a , Krzysztof Kierzek b ,
Matthias Meffert c , Dagmar Gerthsen c , Jerzy Kaleta a , Justyna Krzak a,∗
a
Department of Mechanics, Materials and Biomedical Engineering, Wroclaw University of Science and Technology, Wroclaw, Poland
b
Department of Polymer and Carbonaceous Materials, Wroclaw University of Science and Technology, Wroclaw, Poland
c
Laboratory for Electron Microscopy, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Simultaneous sol-gel process and

phase separation as a new method of
synthesis of SiO2 -PVA hybrid meso-
porous aerogel.
• Their elasticity is associated with the
bulk density by a power-law depen-
dence.
• Including of silica into the PVA net-
work increases the specific surface
area.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, a novel approach of silica-PVA hybrid aerogel synthesis is presented based on the simul-
Received 11 March 2020 taneous sol-gel reaction of the silica precursor tertramethoxysilane (TMOS) and thermally impacted
Received in revised form 3 July 2020 non-solvent induced phase separation of polyvinyl alcohol (PVA). The method based on: (1) water from
Accepted 21 July 2020
PVA solution is required for hydrolysis of TMOS; (2) methanol from TMOS solution, is a non-solvent for
Available online 12 August 2020
PVA. In the result of sol-gel reaction, phase separation and drying during extraction with supercritical CO2 ,
the hybrid SiO2 -PVA aerogels were obtained. Results indicated that, incorporation of the silica network
Keywords:
into the PVA network caused an increase of the specific surface area up to 618 m2 /g from 38.3–110 m2 /g
Hybrid aerogel
Sol-gel
for pure PVA. The Young’s modulus was associated with the bulk density. The obtained hybrid SiO2 -PVA
Phase separation aerogels are a result of two phenomena – the chemical reaction of silica precursor (sol-gel process) and
Silica the physical transformation in PVA solution (phase separation).
Polyvinyl alcohol © 2020 Elsevier B.V. All rights reserved.

1. Introduction

Sol-gel chemistry allows obtaining a wide range of materials,

including thin films, particles or aerogels with many poten-
tial applications [1–9]. A large group of sol-gel materials is
∗ Corresponding authors. based on silicon alkoxides, e.g. tetramethoxysilane (Si(OCH3 )4 )
E-mail addresses: bartosz.babiarczuk@pwr.edu.pl (B. Babiarczuk), or tetraethoxysilane (Si(OC2 H5 )4 ). Under appropriate conditions,
justyna.krzak@pwr.edu.pl (J. Krzak).

https://doi.org/10.1016/j.supflu.2020.104997
0896-8446/© 2020 Elsevier B.V. All rights reserved.
2 B. Babiarczuk, D. Lewandowski, A. Szczurek et al. / J. of Supercritical Fluids 166 (2020) 104997
e.g. precursor:solvent ratio, precursor:water ratio, catalyst (pH),
running reactions lead to the formation of a gel composed of a
silica network with pores filled with liquid [10–13]. The drying
process of the gel, under the supercritical drying, ensures obtain-
ing the aerogel. As a result, silica aerogels known as the lightest
known solid materials were obtained, [8,14–18]. These numerous
extraordinary properties as high specific area, low density, low
thermal conductivity, low dielectric constant and low sound veloc-
ity make them very attractive for various applications, e.g. thermal
and sound insulation, chemical engineering, biomedicine and phar-
macy, space technologies [16,17,19–26].
It should be noted that native silica aerogels are very brittle,
which limits their real-world applications. However, several meth-
ods used to strengthen their structure have already been developed,
and some new ones are on the way [27,28]. Among them is the
aging of the gels [29–32], use silica precursors ensured more flex-
ibility of the network [33–38] or incorporation of polymers into
silica aerogels networks [39–46]. On the other hand, there is more
and more research on biopolymer-based aerogels, e.g. alginate,
cellulose, lignin, pectin, chitosan and proteins [47,48]. Another
example of a biopolymer is polyvinyl alcohol (PVA) which is one
of the very few water-soluble vinyl polymers [49]. There is a very
interesting method for fabricating PVA monoliths called thermally
impacted non-solvent-induced phase separation (TINIPS) [50–53].
Along with adding of the non-solvent (e.g. methanol) to water PVA
solution, in the mixture formed the polymer-rich phase and the
polymer-lean phase. When the amount and distribution of the non-
solvent in the mixture is proper, the system is in metastable state
and phase separation can occur. During the cooling of the mixture
the skeleton is formed from the polymer-rich phase and pores are
generated from polymer-lean phase [50]. In result the aerogel-like
PVA monolith is obtained.
It is well known that silica based on the sol-gel precursor (e.g.
TEOS) is able to bond with PVA chains by the connection between
the silanol groups and the hydroxyl group of PVA via hydrogen
or covalent bonds [54,55]. In the literature, a few synthesis exam-
ples of similar hybrid aerogels or porous materials are showed.
H. Sun et al. [56] presented their synthesis method of PVA-silica
nanocomposite aerogels based on two stages. First, the microp-
orous PVA aerogel via ice templating was prepared, and then a
conformal silica-nanoparticle coating was grown on the PVA scaf-
fold [56]. Another example was published by K. J. Lee et al. [57].
They presented the synthesis of silica aerogel blankets based on
the impregnation of silica aerogel slurry in a mixed ethanol-water
solution. However, they used only a commercially available silica
aerogel powder. An equally interesting material based on direc-
tional freezing to prepare aligned porous structures from PVA and
silica nanoparticles was proposed by H. Zhang et al. [58]. The phase
separation that occurs during the freezing process was a source
for the aligned pore structure. However, in this case, the finally
formed structure was built only from an organic PVA network
and the pores were in the range of macroporous materials. H. M.
Kim et al. [59] presented silica-PVA aerogel insulation composites
synthesis based on mixing a commercially available silica aerogel
powder with a PVA solution. The formation of the SiO2 -PVA aero-
gel hybrid occurred during phase separation. Although the product
volume was smaller than after reagents mixing as a result of sol-
vent vaporization, the porosity of the silica aerogel was preserved.
In comparison to the above-presented synthesis procedures, our
methodology, starting from a silica precursor and PVA solution,
allows to obtain two components of the nanohybrid SiO2 -PVA aero-
gels without the use of pre products.
Our goal was to create a new approach to SiO2 -PVA hybrid
aerogels synthesis and their structural characterization. In this
study, the formulation of the inorganic and organic porous net-
works is proposed - the silica precursor undergoes the sol-gel
Table 1
Nomenclature and composition of the samples.
Sample name TMOS:MeOH:H2 O:NH4 OH:PVA mass ratio PVA [mg/mL]
P60 S0.06 cat 1.0 : 3.2 : 3.3 : 0.002 : 0.49 60
P60 S0.06 1.0 : 3.2 : 3.3 : 0.0 : 0.49 60
P60 S0.1 cat 1.0 : 2.1 : 2.4 : 0.002 : 0.49 60
P60 S0.1 1.0 : 2.1 : 2.4 : 0.0 : 0.49 60
P100 S0.1 cat 1.0 : 2.1 : 2.4 : 0.002 : 0.82 100
P100 S0.1 1.0 : 2.1 : 2.4 : 0.0 : 0.82 100
process, whereas the PVA participates in the thermally impacted
non-solvent-induced phase separation. It was shown that these
processes could occur in one place and at the same time.
2. Experimental
2.1. Materials
To obtain the sol, the following substances were used: tetram-
ethoxysilane (TMOS; 98 %, Sigma-Aldrich) as a silica precursor,
polyvinyl alcohol (PVA, MW: 14000, degree of hydrolysis 94 %,
BDH Laboratory reagents), methanol (MeOH; 100 %, Avantor Per-
formance Materials Poland) as a solvent and non-solvent, water
(H2 O, demineralized). Moreover, one group was synthesized under
catalyst conditions, ammonium hydroxide (NH4 OH; 25 %, Chem-
lab). In Table 1, the used reagents, nomenclature, mass ratios and
PVA concentrations of all prepared samples are presented.
2.2. Methods
2.2.1. Synthesis
Firstly, PVA powder was dissolved in water (∼95 ◦ C) for approx-
imately 2−3 h in two concentrations (60 and 100 mg/mL). The
dissolution was performed under continuous stirring (∼250 r.p.m.)
conditions to form homogeneous PVA solution. After that, the solu-
tion was cooled to 60 ◦ C. In another beaker, TMOS was dissolved
in MeOH solution (with or without ammonia catalyst) and next
it was added dropwise to PVA solution (still 60 ◦ C) under stirring
conditions. After 2−3 min of stirring the homogeneous mixture
was poured into cylindrical molds and protected with Parafilm to
prevent solvent evaporation. The samples were kept at room tem-
perature (21 ◦ C) for 24 h. Meanwhile, the sol-gel reaction and the
phase separation took place. As a result, white light blue monolithic
samples of SiO2 -PVA hybrid gels were obtained. Before drying, to
prevent samples from cracking, the solvent in the monoliths was
replaced by methanol in which it was immersed (3–4 times). Subse-
quently, the samples were put into an autoclave (Paar Mini Bench
Top Reactor 4563) and methanol in the alcogels was replaced by
liquid CO2. Finally, supercritical CO2 drying was conducted (37 ◦ C,
90 bar) and, as a result, hybrid SiO2 -PVA aerogels were obtained.
The synthesis procedure is shown in the scheme below (Fig. 1).
2.2.2. Measurements
For the determination of the porous structure of the samples,
nitrogen gas adsorption at 77 K (ASAP 2020, Micromeritics) was
conducted. Before the measurement, the samples were outgassed
(90 ◦ C, 3 h, < 1 ␮mHg) to remove adsorbed species. The total
pore volume (VT ) was calculated from the amount of the nitro-
gen absorbed at 0.96 p/p0. The BET theory was used to determine
the specific surface area (SBET ). The pore size distribution was plot-
ted according to the NLDFT analysis (cylindrical pores kernel). The
average pore diameter (L) was estimated by a simple formula of
4·VT /SBET , assuming the cylindrical shape of pores.
The surface morphology of the hybrid aerogels was analysed
using scanning electron microscopy (SEM, Hitachi S-3400 N). Due
to the low electrical conductivity of the samples, before the SEM
 B. Babiarczuk, D. Lewandowski, A. Szczurek et al. / J. of Supercritical Fluids 166 (2020) 104997
Fig. 1. SiO2 -PVA hybrid aerogels synthesis procedure.
Fig. 2. Nitrogen adsorption-desorption isotherms and pore diameter distribution of P60 S0.06 /cat (left), P60 S0.1 /cat (middle) and P100 S0.1 /cat (right) hybrid aerogels.
measurements, the surface of the samples was coated with a thin
gold layer by a sputter coating machine (Quantachrome).
Transmission electron microscopy (TEM) analysis of TMOS silica
based native and hybrid aerogels was performed in an aberration-
corrected transmission electron microscope (FEI Titan3 80–300)
operated at 300 keV. TEM samples were prepared by scraping of
tiny aerogel pieces with a scalpel and depositing them on TEM
grids covered with an ultrathin amorphous carbon film (Ted Pella).
Images were recorded with a large defocus due to the weak contrast
of the material.
The chemical structure was determined by Raman spectroscopy
(dispersive Raman Spectrometer, LabRAM HR800 Horiba Jobin
Yvon). The incident laser excitation was provided by a water-
cooled argon laser source operating at 514.5 nm. The spectra were
recorded in the region of 4000–50 cm−1 with a spectral resolution
of 2.5 cm−1 .
The mechanical study was conducted in a uniaxial compression
test (Bionix, MTS Systems Corp.). It was very important to ensure
that the end surfaces of the samples were smooth and parallel. For
this purpose, the end surfaces were shaped with a high speed cir-
cular saw. The mechanical tests were conducted under ambient
conditions. The speed of compression was 1 mm/min. The Young’s
modulus was determined from the linear region of the stress-strain
curve.
The bulk density was determined by the simple weighing of
aerogel samples and measuring their dimensions with callipers.
The linear shrinkage ( ϕ) was measured according to the equa-
tion ϕ = (d0 − d)/d0 [%] where d0 is the initial diameter of the
alcogel and d is the final diameter of the aerogel.
3. Results
Table 2 presents the physical properties of the obtained hybrid
aerogel samples. It can be seen that regardless of the silica precur-
sor and PVA concentrations, the linear shrinkage (diameter) ␸ of
the samples after drying is related with the presence of the cat-
3
alyst. The basic catalyst induces the increases of linear shrinkage
in all three sets of the samples (in terms of the catalyst presence).
However, the differences in linear shrinkage (diameter) values are
clearly smaller and similar in the case of the samples with the cata-
lyst, regardless of the TMOS and PVA concentrations. In the absence
of the catalyst, the higher the TMOS and PVA concentrations, the
lower the shrinkage. There is no clear relation between the TMOS
and PVA concentrations and the shrinkage of the samples in the
presence of the catalyst.
Moreover, in each set of the samples, in terms of the catalyst
presence, the bulk density values are related to linear shrinkage
values - the higher the shrinkage, the higher the bulk density.
However, it is noteworthy that a clear trend can be observed in
the changes of the TMOS and PVA concentrations - the higher the
TMOS and PVA concentrations, the higher the bulk density. In other
words, the more mass in a unit volume (increasing TMOS and PVA
concentrations) the higher the bulk density. In order to reduce the
influence of the shrinkage on the bulk density value, the corrected
(theoretical) density (corr ) were calculated according to the equa-
tion [60] and presented in the Table 2:
corr = b · (1 − ϕ)
where corr is corrected density, b is bulk density and ϕ is linear
shrinkage. After correction the values are lower, however the trend
is still the same.
Porosity parameters are collected in Table 2. All adsorption-
desorption isotherms (Fig. 2) can be classified as type IV, which
demonstrates that they are mesoporous materials. The shape of
hysteresis loops is H1 indicating that the SiO2 -PVA hybrid aerogels
have cylindrical pores and a narrow range of uniform mesopores
[61,62]. It can be observed that values of a specific surface area are
related with the presence of the catalyst whose presence increases
them. There is a strong dependence between the TMOS and PVA
concentrations, and the specific surface area values. Firstly, with an
increase in TMOS concentration (S0.06 vs S0.1), the specific surface
area grows. Secondly, with an increase in PVA concentration (P60
4 B. Babiarczuk, D. Lewandowski, A. Szczurek et al. / J. of Supercritical Fluids 166 (2020) 104997
Table 2
Physical properties of SiO2 -PVA hybrid aerogel samples.
Sample name SBET [m2 /g]a VT [cm3 /g]b
P60 S0.06 cat 598 ± 24 1.81 ± 0,04
P60 S0.06 517 ± 19 0.96 ± 0,02
P60 S0.1 cat 618 ± 23 1.52 ± 0,03
P60 S0.1 584 ± 29 1.06 ± 0,02
P100 S0.1 cat 494 ± 22 1.15 ± 0,02
P100 S0.1 489 ± 21 1.04 ± 0,20
a
(SBET ) specific surface area, b (VT ) total pore volume < 50 nm, c (L) average pore diameter < 50 nm, d (E) Young modulus, e (b ) bulk density, f ( ␸) linear shrinkage (diameter),
g
(corr ) theoretical density calculated according to [60].
Fig. 3. SEM micrographs of P100 (right), P100 S0.1 (middle) and P100 S0.1 cat (left) samples. Scale bar 5 ␮m.
vs P100), the specific surface area clearly drops. The presence of
the catalyst causes much better porosity development of aerogels
– especially total pore volume and average pore diameter. However,
the effect is not proportional to any component concentration and
is the most pronounced in the case of P60 S0.06 cat. Finally, with
the increase in the TMOS and PVA concentrations, the differences in
the specific surface area values in terms of the catalyst presence are
smaller. The increase in the silica precursor concentration (S0.06 vs
S0.1) causes a decrease in the average pore diameter. Meanwhile,
the increase in PVA concentration (P60 vs P100) does not have such
a strong influence on that feature. All aerogels show bimodal pore
diameter distribution (Fig. 2). Most of the porosity is placed in the
range of 3 and 30 nm. However, the contribution of microporosity
in the range of 1.2–1.8 nm is also significant.
The SEM analysis showed that with the incorporation of the
silica network into the PVA network, considerable changes in
the morphology of the aerogels are observed. In Fig. 3, it can be
observed that the native PVA aerogel has macro diameter pores (left
micrograph). The hybrid SiO2 -PVA aerogel without a catalyst (mid-
dle micrograph) is characterized by smaller diameter pores, while
in the presence of the catalyst (right micrograph) the pore diameter
is definitely reduced. Moreover, much smaller particles are visible
in hybrid aerogel, especially in the presence of the catalyst, in com-
parison to the native PVA aerogel. The SiO2 -PVA hybrid without the
catalyst can be considered as an intermediate state between PVA
native and SiO2 -PVA hybrid with the catalyst in terms of the range
of pores and size of the particles.
The TEM analysis provided information about the microstruc-
ture of the P100 S0.1 cat hybrid aerogel on a nanometer scale.
In Fig. 4 (left), the hybrid nature of the SiO2 -PVA aerogel can be
observed. The inorganic silica-based part of the aerogel derived
from silica can be well recognized and the particle size estimated
to about 10 nm. This size range is in good agreement with the sec-
ondary particles size of the native TMOS based silica aerogels in
Fig. 4 (right). Between the silica particles in the hybrid aerogel,
larger amorphous regions with different image contrast are visi-
ble. One of these regions is marked by a dashed line in Fig. 4 (left).
Since this was not observed in the native TMOS based silica aero-
gel, these areas are considered as an organic component based on
PVA.
L [nm]c E [MPa]d b [g/cm3 ]e ␸ [%]f corr [g/cm3 ]g
12.1 ± 0,75 6.43 0.211 23 0.163
7.4 ± 0,43 2.12 0.164 17 0.136
9.8 ± 0,56 6.55 0.230 20 0.184
7.2 ± 0,50 2.97 0.183 13 0.159
9.3 ± 0,58 13.77 0.267 21 0.211
8.5 ± 2,00 4.12 0.190 11 0.170
The Raman spectra of SiO2 -PVA, PVA and SiO2 aerogels (Fig. 5)
confirm the creation of assumed structures - SiO2 -PVA mix, PVA
and SiO2 , respectively. Spectra contain bands characteristic for PVA
- C–H stretching at 2912 cm−1 , C C stretching at 856 cm−1 and
918 cm−1 , mixture of C C and C O stretching at 1094 cm−1 and
1148 cm−1 , mixture of C–H and O H bending at 1444 cm−1 and
broad band with maximum at 1367 cm−1 [63–65]. In the spec-
trum of SiO2 -PVA hybrid aerogel additionally bands, confirming
SiO2 presence, are observed at 440 cm−1 , 817 cm−1 , 1125 cm−1 and
1305 cm−1 , which are characteristic respectively for Si-O-Si rock-
ing, bending and stretching and also at 983 cm−1 characteristic for
Si−OH symmetric stretching [66]. In the spectrum of hybrid aero-
gel also band characteristic for C–H stretching at 2979 cm−1 [67],
which come from unhydrolysed precursor’s groups, appears and
can be interpreted as shifted band at 2963 cm−1 from the SiO2
aerogel. Big decrease in intensity of band characteristic for Si−OH
at 983 cm−1 [66] for hybrid aerogel, in comparison to SiO2 aero-
gel, can reveal reaction of these groups. Big increase in intensity
of band characteristic for Si-O-Si at 817 cm−1 can indicate fur-
ther condensation of silica in hybrid form. On the other hand,
the appearance of weak band at 374 cm−1 , characteristic for Si-O-
C asymmetric deformations [67], can suggest chemical reactions
of silica with PVA. However, the broad band at this wavenum-
ber in spectrum of SiO2 aerogel and similarities in wavenumbers
characteristic for Si-O-C and silica does not allow an unequiv-
ocal statement if chemical reaction between two components
in hybrid aerogel for certain occurs. Complementary measure-
ments by FTIR could confirm possible chemical bonds between
PVA and SiO2 , as was the case mentioned by Karthikeyan et al.
[68].
The microstructure and composition of a material determines
many of its physical, and all of its mechanical, properties [69].
The mechanical tests showed that the molar ratio (TMOS:MeOH),
the PVA concentration and the synthesis conditions (catalyst) have
a strong influence on the mechanical properties of the PVA-SiO2
hybrid aerogels. In Fig. 6, the stress-strain curves from the uniax-
ial compression tests and the photographs of the sample during
compression and its plastic deformation are presented.
From the linear region of the stress-strain curves (Fig. 7) Young’s
modulus (E) values were calculated to describe the elastic proper-
 B. Babiarczuk, D. Lewandowski, A. Szczurek et al. / J. of Supercritical Fluids 166 (2020) 104997 5

Fig. 4. TEM micrographs of P100 S0.1 cat hybrid aerogel (left) and TMOS based silica native aerogel (right). Scale bar 20 nm and 50 nm, respectively.

Fig. 5. Raman spectroscopy of hybrid SiO2 -PVA aerogel (P100 S0.1 cat), PVA aerogel (P100) and SiO2 aerogel, blue, red and black respectively.

Fig. 6. Stress-strain cures as the result of hybrid SiO2 -PVA aerogels uniaxial com-
Fig. 7. Initial parts of the stress-strain curves with linear regions corresponding to
pression.
elasticity.

ties of the aerogels. The calculations according to the formula, were

performed in the following way: the higher the PVA concentration, the higher the Young’s modulus.
It is well known that a higher content of silica precursor in aerogel
stress
E= = slope of stress versus strain curve provides higher stiffness, hence Young’s modulus is higher as well.
strain The obtained results confirmed this mechanical feature of aero-
The obtained values of Young’s modulus are presented in gels and with the increasing TMOS concentration, higher values of
Table 2. Firstly, a clear division between the aerogel samples with Young’s modulus are observed.
and without a catalyst can be observed. The base catalysis synthe- In Fig. 8, the relationship between Young’s modulus and density
sis provided materials with a higher Young’s modulus. Additionally, of the hybrid aerogels was presented. The mechanical properties
6 B. Babiarczuk, D. Lewandowski, A. Szczurek et al. / J. of Supercritical Fluids 166 (2020) 104997
Fig. 8. Young’s modulus as a function of SiO2 -PVA hybrid aerogel density (log-log
plot).
of the hybrid aerogels are described as a function of their den-
sity according to the power-law dependence, E ∝ ˛ , with scaling
exponent ˛ = 3.78 ± 0.33.
4. Discussion
Our idea for using the PVA for cross-linking the SiO2 aero-
gel structure was born after the observation that methanol can
be used as a non-solvent [51]. In the sol-gel process, the alco-
hol (e.g. methanol) is a co-solvent and a by-product of hydrolysis
and condensation reactions. Water contained in the PVA solution
is necessary for hydrolysis of the silica precursor. Therefore, our
hypothesis about the possibility of the simultaneous sol-gel reac-
tion of the silica precursor and phase separation of the PVA is very
likely. Below in Fig. 9 the proposed mechanism of the simultane-
ous sol-gel reaction and thermally impacted non-solvent induced
phase separation is presented.
The resultant hybrid aerogel preserves the mesoporosity of the
TMOS based native silica aerogel. Simultaneously, for the proper
phase separation between the immiscible polymer water phase and
the alcoholic non-solvent a volume ratio of 2:3 is required, as in the
case of pure PVA monolith based on methanol as the non-solvent
[51].
The incorporation of various additives into PVA the network
exerts significant influence on the specific surface area (SSA). Other
authors reported that pure PVA monoliths / aerogels are charac-
Fig. 9. Proposed mechanism of simultaneous sol-gel reaction and TINIPS.
terized by SSA in the range of 38.3–110 m2 /g [50,51,53,56,70–72].
Meanwhile, the hybrid PVA aerogels can demonstrate clearly
higher values of SSA, e.g. for PVA hybrid aerogels modified with
cellulose nanofibrils and/or graphene oxide nanosheets they are
in the range 190–243 m2 /g [72]. For PVA modified with SiO2 con-
formal coatings, the SSA values are in the range of 48.8–476.5 m2 /g
and the higher the silica precursor (TEOS) concentration, the higher
SSA [56]. H. M. Kim et al. [59] presented silica-PVA composite aero-
gels with the SSA values in the range of 1–355 m2 /g in accordance
with the decreasing concentration of PVA from 20 wt% to 3 wt%.
Similar trends were observed in our SiO2 -PVA hybrid aerogels, i.e.
the smaller PVA concentration and the higher silica concentration,
the higher SSA. However, in comparison to the above examples of
hybrid aerogels, ours are characterized by higher values of SSA, in
the range of 489–618 m2 /g.
Mechanical properties of the aerogels are often presented from
the point of view of their density. The relationship between Young’s
modulus and density for highly porous materials is described by the
power law, E ∝ ˛ , where E is Young’s modulus,  is density and
˛ is the scaling exponent. Depending on the nature of the aerogel
network, the scaling exponent ˛ typically is in the range 2.5–4.0
[73]. The value of ˛ for silica aerogels was presented by several
authors – in experiments, it was in the range of 2.85–3.90 [74–81],
and in computational simulations, it was in the range of 3.11–3.84
[82–87]. The scaling exponent obtained from the uniaxial compres-
sion of our silica-PVA hybrid aerogels (˛ = 3.78 ± 0.33) is in line
with the above presented previous results for aerogels.
Differences in the value of shrinkage between hybrids were
observed, whose synthesis with or without a basic catalyst was
conducted. Slightly higher shrinkage in the base catalysed hybrid
aerogels were observed. The phenomena responsible for the
shrinkage of the gels during drying are complex. However, they are
mainly related to capillary pressure exerted by pore liquid and the
modulus/rigidity of the solid matrix [88,89]. Generally, the increase
in the average pore size reduces the capillary pressure. However, it
also leads to a decrease in the solid content or increase in particle
diameter and also, consequently, degrades the mechanical proper-
ties [90]. The prepared hybrid aerogels are composed of inorganic
and organic networks, which can lead to non-homogeneous pore
size distribution. In our opinion, further research into the influ-
ence of the pH in a wider range of its values on the shrinkage of
hybrid aerogels is necessary. Moreover, the consideration of the
aging process and its conditions in future research is crucial because
it would provide a decrease in shrinkage during aerogel drying
[29,30,32,91,92].
5. Conclusions
We presented a novel approach to the synthesis of the SiO2 -PVA
hybrid aerogels and characterized their physicochemical prop-
erties. The synthesis is based on the sol-gel transition of the
 B. Babiarczuk, D. Lewandowski, A. Szczurek et al. / J. of Supercritical Fluids 166 (2020) 104997
silicon alkoxide and the thermally impacted non-solvent induced
phase separation of the water-soluble polymer. It was shown that
the physicochemical properties, including microstructure, porosity
and Young’s modulus, can be controlled by changing the compo-
sition of the reaction mixture. The proposed method is quite easy
and fast. In our opinion, such an approach can be useful and flex-
ible in a wide range of materials. There is enormous potential in
the use of this procedure with organoalkoxysilanes, other polymers
and non-solvents. In addition, polymer cross-linking can provide
more benefits, especially in terms of mechanical properties. More-
over, the hydrophobization process could enable ambient pressure
drying.
The obtained hybrids materials may find application in the field
of energy storage or heat insulation [93] where the properties of
inorganic part of aerogel – SiO2 , connected with their high poros-
ity and huge specific surface area are extremely important but the
poor mechanical strength limits their direct use. The most impor-
tant fact in case of application of the obtained hybrids is that the
properties of huge surface area derived from the inorganic part
are, with some limitation, transferred to the final material, and
mechanical reinforcement provided by the organic part may allow
processing and application of the hybrid materials. Generally in the
hybrid materials, advanced is also that the organic part of aerogels
allows incorporation of inorganic part with or without chemical
interaction, depending on requirements.
The properties of obtained hybrid materials may also be impor-
tant in acoustic insulators, catalyst supports, mainly because of high
surface area, and obtained chemical composition makes additional
attractiveness for drug delivery systems.
Declaration of Competing Interest
The authors report no declarations of interest.
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