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Flexibilisation of resorcinolformaldehyde aerogels

Cite this: J. Mater. Chem. A, 2013, 1,
13462

Marina Schwan* and Lorenz Ratke

Ambient pressure dried resorcinolformaldehyde (RF) organic aerogels are usually hard and brittle with
Young's moduli in the range of 12 MPa, strengths of about 100 kPa and densities in the range of 0.2
to 0.4 g cm
3. Modications of the classical solgel synthesis route, transform these brittle materials into
rubber- or cork-like exible aerogels. We observed that in a small window of process parameters, the
aerogel density decreases by an order of magnitude as well as the Young's moduli and the compression
strengths. These new types of RF aerogels are elastically deformable by more than 40% in an almost

Received 12th August 2013

Accepted 6th September 2013

reversible manner. In this paper we describe the eects of various solgel parameters on the exibility,
such as resorcinol to water and catalyst molar ratio and the pH of the initial solution. The aerogels are
characterized with respect to the envelope density, stressstrain behavior and microstructure as

DOI: 10.1039/c3ta13172f

observed from SEM fractographs. The chemical structure and structural dierences arising between

www.rsc.org/MaterialsA

brittle and exible RF aerogels were studied by recording

Introduction

Aerogels are highly porous, low density materials with fascinating properties. Their bulk density lies in the range of 0.03
0.5 g cm
3 and they possess a thermal conductivity value under
ambient conditions as low as 0.012 W m
1 K
1 and low sound
velocity, which leads to various applications, such as in thermal
and acoustic insulators.1 The high specic surface area and the
conductivity of carbon aerogels open a further important eld
of application, namely for batteries or fuel cells.2 Resorcinol
formaldehyde aerogels, rst reported by Pekala, are organic
aerogels which are synthesized by the polycondensation of
resorcinol with formaldehyde, forming a three-dimensional gel
network.3 Usually the resulting gel is dried under the supercritical conditions of an organic solvent which is used to
exchange the reaction by-products such as water and also the
unreacted monomers. Various articles have reported the eects
of process parameters like the pH value,4 resorcinol to formaldehyde (R/F) ratio, resorcinol to water (R/W) ratio, concentration and type of catalyst (R/C) ratio,1,5 and the drying routine6 on
the physical and chemical properties of the resulting RF aerogel. Typically for supercritically dried RF-aerogels a high catalyst
concentration R/C ratio of around 50 to a few hundreds is used.
Fricke et al. were the rst to describe a synthesis route for RF
aerogels utilizing ambient drying.7 They observed that at
constant R/W and R/F ratios, a variation of R/C leads to gels
which can be dried under ambient pressure. The authors found
that the gels could be dried under ambient pressure if the R/C
ratio is higher than 1000. The ambient-dried aerogels have
Institut f
ur Materialphysik im Weltraum, DLR, 51170 Cologne, Germany. E-mail:
Marina.Schwan@dlr.de; Lorenz.Ratke@dlr.de; Fax: +49 2203 61768; Tel: +49 2203
601 3749; +49 2203 601 2098

13462 | J. Mater. Chem. A, 2013, 1, 1346213468

13

C-NMR spectra.

typically a higher density, i.e. 0.2 to 0.4 g cm
3, and their

microstructure is not really nanostructured but the building
particles of the 3D network are in the range of 100 to 1000 nm.
This development opened especially new elds of applications, since ambient drying eases production compared to
supercritical drying. Applications for instance include the use of
RF aerogels in foundries8 or as a ller for vacuum isolation
panels.9
All RF aerogels reported so far are brittle and fragile; they
break easily and hence this limits their area of application. To
the best of our knowledge there is no report in the literature on
the RF aerogels being exible like rubber.
The present paper describes a route to synthesize exible RF
aerogels. The aerogels obtained are characterized by density
measurements, compression tests, SEM and 13C-NMR.

Experimental section

2.1

Materials and synthesis

The exible RF aerogels were produced by a base catalyzed sol

gel process followed by the ambient pressure drying. The
chemicals used were resorcinol (98%, Aldrich), formaldehyde
(37% in water, stabilized with 10% methanol, Merck), sodium
carbonate anhydrous (Aldrich) and 2.0 N nitric acid (standardized solution, Alfa Aesar). Deionized water was employed in the
synthesis. Acetone (pure, technical grade, Th. Geyer) was used
for washing the gels prior to ambient drying.
The R/W molar ratio was systematically varied from 0.005
to 0.013. The R/F molar ratio was xed at 0.5. The molar
ratio of R/C was xed at a value of 50. Gelation did not occur
with R/C ratios higher than 50. In a typical synthesis of gel with
R/W 0.008, 5.0 g of resorcinol was dissolved in 97.5 g of
deionized water and 7.4 g of formaldehyde was added. The

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solution was stirred for further 5 minutes and then 0.096 g of
sodium carbonate was added. Aer further stirring, the pH was
adjusted in the range 5.45.6 with 0.50.6 mL nitric acid. The
whole preparation of the solution was carried out at room
temperature. The solution was stirred, and the container was
sealed and placed in an oven maintained at 80  C for one week.
Aer one week, the gelled solution changed its color from
transparent to orange/orange brown. The solution was taken
out of the oven and cooled to room temperature. The gel was
washed for 3 days with acetone and the nal drying was done in
an oven maintained at 80  C. Aer 24 h, the dried gel was
exible and did not show any measurable shrinkage.
A hard and brittle RF aerogel was produced to carry out
comparative investigations, such as density, Young's modulus
determination and 13C-NMR examination. The aerogel was
prepared under the same conditions (R/C 50 and R/F 0.5)
described above and only a dierent R/W molar ratio (0.044) was
used. This gel was also dried under ambient pressure at 80  C.
An additional set of samples was prepared where the pH was
varied in the range 4.357.5 to study its eect on aerogel
properties.
2.2

Characterization

The chemical structure of the exible aerogel was investigated by

recording 13C-NMR spectra CP-MASS with TOSS. The experiments were carried out with an Avance 400 spectrometer from
Bruker (University of Duisburg-Essen, Germany) with 400 MHz.
Scanning electron micrographs (Merlin, Zeiss) were used to
determine the pore and particle size and also to study the
structure of aerogels. The RF samples were sputtered with gold
before imaging. The bulk densities were calculated by their mass
to volume ratio. Young's modulus was determined by uniaxial
compression tests with a Chatillon TCD 200-SS Ametek machine.
The cylindrical samples of 1525 mm height were compressed up
to 40% of their original height with a small piston (diameter
1 mm). Aer some time the height was measured again and
compared with the original height. Young's moduli were calculated from the slopes of the stresscompression curves.

Journal of Materials Chemistry A

Fig. 1 Ternary diagram showing the impact of water amount on the properties
of aerogels in the resorcinolformaldehydewater system.

led to hard, compact aerogels. They exhibit no exibility. The

ternary diagram shows that the exible RF aerogel could be only
produced in the range R/W 0.0060.01 (0.9940.990 mol%
water). The aerogels in this R/W molar ratio range are exible: they
can be bent and deformed easily and revert back to the original
shape upon release of pressure like rubber as shown in Fig. 2.
These aerogels endure up to 40% linear compression and then go
back to 90% of their original height. Aerogels produced with a R/W
molar ratio higher than 0.01 (0.9890.987 mol% water) are corky,
since their haptic impression reminds us of natural cork.
The ternary diagram of the resorcinolformaldehydewater
system shows a discontinuous change in the mechanical
properties of RF aerogels with respect to the water amount at
constant R/F and R/C molar ratios. In the range of 0.990
0.994 mol% very small changes of 0.001% water lead to nonexible aerogels. Schaefer and Pekala observed that both the
solid concentration and catalyst amount aect the mechanism
of phase separation leading to the gel formation.10,11 They
reported about two dierent mechanisms with which phase
separation
occurs:
nucleation-growth
and
spinodal

Results and discussion

It was observed during our study that exible aerogels could be

obtained if the solid concentration in the initial solution is very
small. The R/W molar ratio was varied in the range 0.0050.013,
while the R/C and R/F molar ratios were constant. We also
observed that the pH value has an eect on the exibility when
the pH was varied in the range 4.357.5. The following sections
describe how these variations of the synthesis route aect the
aerogel properties.
3.1 Eect of R/W molar ratio on the mechanical properties
and pore structure
RF aerogels synthesized in the range R/W 0.0050.013 (0.995
0.987 mol% water) showed dierent mechanical properties and
are represented in the ternary diagram provided in Fig. 1. A high
dilution of the initial solution (R/W 0.005, 0.995 mol% water)
This journal is The Royal Society of Chemistry 2013

Fig. 2

Flexible RF aerogels produced with the R/W molar ratio 0.008.

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Table 1 Eect of R/W molar ratio on the bulk density, shrinkage and mechanical
properties of aerogels

R/W

Bulk density,
[g cm
3]

Young's modulus,
[kPa]

Shrinkage,
[%]

Mechanical
properties

0.005
0.006
0.007
0.008
0.009
0.010
0.011
0.012
0.013

0.35
0.14
0.09
0.06
0.07
0.08
0.21
0.18
0.22

1290
350
90
65
85
150
950
4838
3120

49
No
No
No
No
No
48
39
45

Hard, brittle
Flexible
Flexible
Flexible
Flexible
Flexible
Corky
Corky
Corky
Fig. 4

decomposition. It is reasonable that in our study the transition

between these two mechanisms occurs in the investigated area,
shown in the ternary diagram (Fig. 1). The small variation of
water amount at a constant catalyst ratio could lead to the
increased tendency of one of the phase separation ways, i.e.
nucleation-growth or spinodal decomposition.
The dierent gel formation mechanisms aect the
morphology of aerogels, which in turn aects the mechanical
properties. As seen from Table 1, exible aerogels produced
with R/W 0.0060.01 show the lowest densities in the range
0.060.14 g cm
3 with negligible shrinkage, while aerogels
synthesized above and below this range are non-exible, shrink
to 4050% and have higher bulk densities.
A stresscompression curve of a exible RF aerogel (R/W
0.008) is provided in Fig. 3. The sample was compressed up to
40% of its original height. At the beginning of the compression
test the porous structure can be deformed elastically. The slope
in this range was used to calculate Young's modulus.12 In this
range of deformation one can hear a noise stemming from
inside the aerogel, probably the cracking of brittle pore walls or
network structures. With a further increase of stress the pore
walls touch and densication begins.
Resorcinolformaldehyde aerogels produced with the R/W
molar ratio in the range of 0.0110.013 show another type of
stresscompression curve. Fig. 4 shows a long linear elastic
range. At a load of 0.45 MPa the slope decreases slightly, and the
sample begins to deform. The stress can be increased further to

Fig. 3

Stresscompression curve of aerogel with R/W 0.008.

13464 | J. Mater. Chem. A, 2013, 1, 1346213468

Stresscompression curve of the aerogel with R/W 0.012.

0.75 MPa with a dierent slope, followed by a plateau of almost

constant average stress level which is interrupted by small
cracks. The sample eventually breaks. It looks as if there are
several dierent slopes. The slopes are marked 1, 2, 3, 4 and 5 as
shown in Fig. 4. The initial slope is 38% higher than slope 2. In
the range 35 the slope decreased by 50% compared to slope 1.
Table 1 shows that Young's modulus of resorcinolformaldehyde aerogels is related to the R/W molar ratio.
Very low Young's moduli of 65350 kPa are typically for
exible RF aerogels produced with an R/W molar ratio in the
range of 0.0060.01. Outside this R/W range larger Young's
moduli are observed. As provided in Table 1, these aerogels have
Young's moduli between 950 and 4838 kPa.
3.2

Eect of the R/W molar ratio on the porous structure

The SEM micrographs of exible and non-exible aerogels allow

to visualize the network and the pore structure obtained by
varying the synthesis route. The microstructures of aerogels
obtained by varying the R/W molar ratio are presented in Fig. 5.
The aerogels which are produced with R/W 0.005, which are
hard, show a porous nanostructure. From Fig. 5a, it can be seen
that the size of the particles is around 4080 nm where the
particles are very dense and interconnected. A similar nanostructure has been observed for the corky type aerogel synthesized
with R/W 0.013 presented in Fig. 5f. The particle size is around
80 nm with a highly cross-linked network. The SEM fractograph of
an aerogel sample with R/W 0.012 is provided in Fig. 5e, which
also leads to the formation of a nanostructure with particle size
around 60 nm. However this aerogel shows an interconnection
with evidence of necks between the particles. Moreover, hard and
corky aerogels show a homogeneous network with mesopores. In
contrast, very small dierences in the water amount make the
aerogels exible and the fractographs are provided in Fig. 5bd.
The images show a coarse structure, with densely packed particles, which stick together via more or less thick polymeric bridges.
For the aerogel sample with R/W 0.007, where the fractograph is
given in Fig. 5b, a heterogeneous network was formed with a few
large-sized spherical particles of about 2 mm and small-sized
particles in the range of 0.40.5 mm.
With increased water amount, the aerogel samples with
R/W 0.008 and 0.009 analog Fig. 5c and d, homogeneous
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Fig. 5

SEM pictures of exible (bd) and non-exible (a, e and f) RF-aerogels produced with dierent R/W molar ratios.

structures were formed. From Fig. 5c it can be seen that big

pores of about 1020 mm and particles of 11.2 mm are formed.
Smaller particles were formed for the aerogel sample with
R/W 0.009 depicted in Fig. 5d where the particle size is about
0.7 mm and pore size about 510 mm. What is remarkable is the
formation of large necks in the structures of exible aerogels.
The microstructures of exible aerogels give the impression
that all particles are covered with a coating of RF, which probably is formed aer network formation.
We conclude that the microstructures as seen in the SEM
images show clear dierences between brittle, exible and corky
aerogels. It seems that the R/W ratio denes the microstructure
of aerogels at given R/F and R/C ratios. Several authors have
reported that the R/W molar ratio aects the nal porous
This journal is The Royal Society of Chemistry 2013

structure. Al-Muhtaseb and Ritter5 have shown that the reduction

of the solid concentration led to an increased particle size and a
reduced density. This result is similar to that observed for exible
aerogels. Yamamoto et al.13 have shown that with decreasing R/W
molar ratio at constant R/C ratio, the peak value of the pore size
distribution increased. To the best of our knowledge there has
been no report on how such signicant, discontinuous dierences in morphology can be generated by small dierences in the
R/W ratio. The question arises of how to correlate the microstructure dierences with dierent mechanical behaviors.
To synthesize RF aerogels with such a high R/C value as in
this present study, one typically would have to supercritically
dry the samples to avoid appreciable shrinkage. We observe
indeed a large shrinkage of around 50%, but not when the

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Journal of Materials Chemistry A

aerogels are exible. Therefore we believe that the mechanism
of microstructure formation is apparently dierent. At a high
R/C value many polycondensation reactions are nucleated
everywhere in the solution building high density oligomers and
particles, which then can agglomerate. The higher the dilution
with water, the farther apart the particles are and the more loose
the network would be. Below the percolation threshold no
gelation would occur, setting a limit to the degree of dilution.
Aggregation and network formation are dierently discussed in
the literature for RF aerogels. Gommes et al.14 performed a
theoretical study, in which they described the network formation as a process of either nucleation-growth or spinodal
decomposition leading to a branched two-phase nanostructured gel. They concluded that currently small angle X-ray
scattering is not able to discern between both possible ways to
yield an aerogel structure. Binder15 also reported two regions in
the temperatureconcentration graph of a binary mixture where
inside the miscibility gap there exist metastable and unstable
regimes. The metastable region starts at a given temperature at
the binodal line when the concentration of the second component is increased and ends at the spinodal being the transition
to the instable regime. We infer that a mechanism of phase
separation in the metastable region would always lead to a
continuous change in the microstructure with dilution (the
large the dilution, the more loose the network and the smaller
the particles). Moreover, with dilution the microstructure would
essentially be the same and only the size of particles should
change. In this range the structure consists of spherical particles in a more or less loose network, as exhibited in Fig. 5a, e
and f. Another type of phase separation occurs in the unstable
region which would lead to a wavelike, branched but connected
structure. Fig. 5bd show that the network formed is relatively
thick micro-range and hence we observed no shrinkage since
the network withstood the capillary stresses.
One could speculate that in the ternary phase diagram of R, F
and W there is a small region at a given temperature in which
spontaneous polycondensation reactions occur leading to a
highly bridged and branched network running through the
whole solution. We further speculate that during polycondensation the miscibility gap shis its critical point and
height depending on the degree of polymerization according to
the FloryHuggins theory. If initially the system is in the
metastable region leading to a particle network, it could move
into or close to the spinodal, since this changes with time and
then initiates the RF-coating observed as a result of spinodal
decomposition.
The R/W ratio is not the only parameter aecting the structure. The pH-value is also essential, which can be adjusted
independently of the amount of catalyst used.

3.3

Eect of pH on the bulk density

The eect of pH in the synthesis of RF aerogels was studied in

detail by Pekala3 and Lin.4 In our experiments we investigated
how the pH value in the range 4.357.5 aects the properties of
exible RF aerogels, while the R/C 50, R/W 0.008 and R/F
0.5 molar ratios were kept constant. We observed, as Fig. 6

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Fig. 6

Eect of pH on the bulk density.

illustrates, that the pH has an inuence on the exibility and

bulk density of aerogels. The gelation did not occur with an initial
pH below 5.0. In this range not sucient number of resorcinate
ions were formed to result in a gel. A pH above 5.65 leads to hard,
shrunken, non-exible RF aerogels with a bulk density of 0.38
0.45 g cm
3. According to Lin's work, the dehydration reaction is
hindered at high pH value. Consequently, a less cross-linked
structure will be created, which collapses during drying leading
to higher bulk density. Only in the pH range 5.055.65 exible RF
aerogels could be produced. It was observed that samples which
were produced with pH 5.055.30 shrunk, compared to samples
at pH 5.435.65, which exhibited no shrinkage. The dehydration
and condensation reactions are suciently promoted in this
range resulting in a high cross-linked, strong structure. This is in
agreement with the studies by Pekala and Schaefer.10,11 They
reported that highly cross-linked and branched structures were
formed at higher pH values. In the pH range 5.055.30, the
number of resorcinate ions decreased leading to a weak crosslinked structure, where the system persisted for a longer time in
the metastable phase before moving to the unstable phase. As
discussed in the previous section, the gel formation mechanism
aects the pore structure and consequently the exibility of the
aerogel. Fig. 6 depicts the bulk density of exible aerogels with
values between 0.06 and 0.09 g cm
3. These results are really
good for ambient dried aerogels which also have negligible
shrinkage.

3.4

Chemical structure of exible and non-exible aerogels

The reaction mechanism of the resorcinolformaldehyde polycondensation is well investigated.4,5,16 First the electrophilic
addition of resorcinol with formaldehyde takes place. In this
process the o- and p-positions of resorcinol will be lled. Then
the condensation of two such molecules starts and the methylene and dimethylene ether bridges are formed as shown in
Fig. 7. The polycondensation of such dimers takes place leading
to a 3D-network.
The described chemical reaction scheme is reected in our
13
C-NMR results. The assignments of RF resonances are based
on the former studies of Mulik et al.,17 Moudrakovski et al.18 and
Rego et al.19 on resorcinolformaldehyde aerogels and phenolformaldehyde polymers. Fig. 8 shows the 13C-NMR spectra
of a exible RF aerogel. The resonance at 151 ppm corresponds
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Journal of Materials Chemistry A

Fig. 9

Fig. 7

13

C-NMR of hard RF aerogels.

Chemical structure of the resorcinolformaldehyde aerogel.

Fig. 10 13C-NMR of exible RF aerogels at room temperature (black line) and

323 K (red line).

Fig. 8

13

C-NMR of exible RF aerogels.

to carbons of the aromatic ring directly attached to a hydroxyl

group. The carbons in p- and o-positions are assigned to resonances at 130 and 119 ppm. The region between 20 and 40 ppm
centered at 28 ppm is attributed to methylene bridges. The
dimethylene ether bridges appear in the range of 6579 ppm.
The resonance 5863 ppm could be assigned to methylol groups
Ph-CH2OH.
Fig. 9 shows the 13C-NMR spectra of a well-known hard RF
aerogel. As expected, the spectra of both aerogels are similar but
slightly dierent. The width and height of the resonances at
around 28 ppm are noticeably dierent. The exible aerogel
exhibits a broader, but low intensity peak in comparison to the
brittle aerogel. The dierence in signal broadness can be due to
two reasons. It is governed by either (1) microscopic mobility of
methylene bridges or (2) by the dierent chemical environments
of CH2-groups formed by op; pp or oo condensation reactions.
If the peaks are broad, it is inferred that CH2 groups are
formed from all the possibilities, i.e. op; pp or oo. If the peaks
are less broad, then the CH2 groups mainly arise only from one
type of bridge, i.e. either op or pp or oo. Moudrakovski et al.

This journal is The Royal Society of Chemistry 2013

also argued in their study that the broadness of the peak is a

result of the inhomogeneity of the linkages among the resorcinol ring.18 13C-NMR investigation at dierent temperatures
could help to separate these two causes. The 13C-NMR spectra
recorded at room temperature and 323 K are provided in Fig. 10
and 11, respectively.
The microscopic mobility will rise at elevated temperature
and the broadness of the peak appearing at 28 ppm is a

Fig. 11 13C-NMR of hard RF aerogels at room temperature (black line) and 323 K
(red line).

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conrmation of the same. We observe that there is no dierence
in the broadness of peaks at higher temperature. Hence we infer
that the exibility may be arising from the dierent chemical
environments of the CH2 groups formed by oo, op and pp
condensation reactions. The mechanical properties meaning
the exibility could then be a result of two eects: (1) the
special microstructure and (2) the larger variety of bonding
between the benzene rings. In a particle built network the necks
between the particles are notches easing crack extension and
leading to a brittle behavior. Once these necks are covered by an
RF-coating, the notches disappear and a exible reaction is
possible, provided the RF-polymer itself is exible or at least has
very low Young's modulus (which is the case). The measured
large variety of possible benzene ring conformations in the
exible RF-aerogels reminds us of the origin of the rubber
elasticity being partly entropic in nature.

Conclusions

Flexible resorcinolformaldehyde aerogels could be synthesized. The water and catalyst amount, pH of the initial solution
are the crucial factors in synthesis of exible resorcinolformaldehyde aerogels. There is only a small window to achieve the
exibility: R/C 50, R/F 0.5, R/W 0.0060.010 and pH
5.45.6. Aer ambient pressure drying the gels prepared in this
small window are exible, possess big particles of about 0.7
1.2 mm, pores in the range of 520 mm, very low densities in the
range of 0.060.01 g cm
3 and low Young's moduli in the range
of 65350 kPa. Experiments showed that a small change in the
molar concentrations of about R/W  0.001 and pH  0.1
resulted in hard or corky, non-exible aerogels. Probably in this
range a transition in the gel formation mechanism occurs, for
instance from the metastable to unstable regime inside the
miscibility gap, which essentially aects the microstructure and
in turn mechanical properties. The 13C-NMR investigation
showed that the exible properties are caused by dierent
possibilities of positioning of methylene bridges between
resorcinol molecules. Flexible aerogels showed a higher inhomogeneity of the linkages among the resorcinol ring. Probably,
this fact promotes a formation of coarse porous structure,
which in turn makes micro deformation of pore walls possible.
In our opinion, both chemical structure as well as pore structure
lead to exibility of resorcinolformaldehyde aerogels.

Acknowledgements
The authors gratefully acknowledge support by Dr Matthias
Kolbe from DLR, Cologne for help with the SEM images
and Professor Dr Christian Mayer from the University of

13468 | J. Mater. Chem. A, 2013, 1, 1346213468

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Duisburg-Essen for
discussions.

13

C-NMR investigations and many helpful

Notes and references

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9 http://americanaerogel.com (accessed Jul 5, 2013).
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