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Flexible aerogels with interpenetrating network

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structure of bacterial cellulosesilica composite

from sodium silicate precursor via freeze drying
Cite this: RSC Adv., 2014, 4, 30453

process
Huazheng Sai,a Li Xing,a Junhui Xiang,*a Lijie Cui,*b Jianbin Jiao,c Chunlin Zhao,a
Zhenyou Li,a Fei Lia and Ting Zhanga

Received 28th March 2014
Accepted 17th June 2014
DOI: 10.1039/c4ra02752c
www.rsc.org/advances
Bacterial cellulose (BC)silica composite aerogels (CAs) with interpenetrating network (IPN) microstructure
are prepared through a permeation solgel process followed by freeze drying. The IPN structure is
constructed by diusing the precursor into a three-dimensional (3D) BC matrix followed by permeating
the catalyst into the BC network gradually to promote the in situ condensation of precursor to form a
SiO2 gel skeleton from outside to inside. The precursor used here is Na2SiO3 instead of traditional
tetraethoxysilane. This IPN structure could oer excellent mechanical properties to aerogels, and is
essential to prepare exible aerogels by freeze drying. The compression modulus of CAs could be
adjusted in the range of 0.38 MPa to 16.17 MPa. The BCsilica CAs exhibit low density (as low as 0.011 g
cm
3), high specic surface area (as high as 534.5 m2 g
1) and low thermal conductivity (less than
0.0369 W m
1 K
1). Furthermore, the contact angle of the hydrophobization modied CAs is as high as
145 . The outstanding hydrophobicity and the large specic surface area endow the hydrophobic CAs
with excellent oil absorption capability on the water surface. Moreover, the hydrophobic CAs that had
absorbed oil could be washed and recycled.

ameliorate the microstructure of silica gel skeleton to improve

Introduction
Aerogels are porous solids made by removing the solvent from
gels while maintaining the porosity of the gel network. They
have an enormous potential to be used in thermal insulation,
optics, acoustic insulation, catalysts and absorbents because of
their low thermal conductivity, low dielectric constant, large
specic surface area and low density.1,2 Unfortunately, the
applications of inorganic aerogels in daily life have been
restricted due to their inherent fragility and high cost.3,4 Hence,
developing an ideal method to prepare aerogels is vitally
signicant to match the demand of their future applications.
Silica aerogel networks are formed by connecting silica
nanoparticles. A few methods have been widely studied to
a
College of Materials Science & Opto-Electronic Technology, University of the Chinese
Academy of Sciences, Yuquan Road 19A, Beijing 100049, China. E-mail: xiangjh@
ucas.ac.cn
b
College of Chemistry and Chemical Engineering, University of the Chinese Academy of
Sciences, Yuquan Road 19A, Beijing 100049, China. E-mail: ljcui@ucas.ac.cn
c
College of Engineering and Information Technology, University of the Chinese
Academy of Sciences, Yuquan Road 19A, Beijing 100049, China
Electronic supplementary information (ESI) available: The photograph of the
CAs which were compressed about 50%, TGA analysis curve, the SEM images of
CAs (# 7) aer being wetted and dried again, the SEM images of CAs (# 7) aer
hydrophobization treatment. See DOI: 10.1039/c4ra02752c
their mechanical strength: increasing the concentration of
precursor to increase the number of connecting points between
the silica nanoparticles,5,6 or using an aging process to make the
silica migrate to the neck regions between two connected silica
nanoparticles to thicken the neck regions in the silica gel
skeleton.79 Recently, Rao et al.10,11 and Kanamori et al.12 used
alkyltrialkoxysilane instead of the traditional tetraethoxysilane
(TEOS) precursor to endow exibility to the silica skeleton,
because the cross-link density of silica could be decreased (the
number of alkoxy groups that can form rigid SiOSi bonds
aer hydrolysis decreased from four to three). Moreover, the
copolymerization or cogelation of silanes with an organic
polymer has been studied to improve the mechanical properties
of silica aerogels.13,14 Especially, Meador et al. have demon-
strated that reinforcing silica aerogels by conformally coating
the silica gel skeleton with a polymer was a more eective way to
improve its mechanical properties.1518 Their excellent studies
improved the strength of aerogels by as much as 2 orders of
magnitude while only doubling the density as compared to
native silica aerogels. Furthermore, they introduced exible
links [e.g. 1,6-bis(trimethoxysilyl)hexane] into the silica skeleton
to reduce the SiOSi bonds followed by the conformal coating
of polymer.19 Both the exible links and the isotropic coating
endow the aerogels with outstanding exibility and recovery

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(they recover nearly 100% of their original size aer compres-
sion to 25% strain twice). However, they pointed out that the
preparation process was fairly involved, and the method of
conformally coating the silica gel skeleton with a polymer was
required to be streamlined to adapt to commercial scale
manufacturing.20
Recently, we have developed a method to construct an
interpenetrating network (IPN) of bacterial cellulose (BC) matrix
and silica gel skeleton.21 It is dierent from the work reported in
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hydrophobicity, because the permeation solgel process used
here enhances the roughness of the sample surface.
The synthesis of BCsilica CAs based on sodium silicate
precursor is illustrated in Fig. 1. First, the pretreated BC
hydrogels were immersed into Na2SiO3 solution at 80  C to make
the precursor diuse into the BC hydrogel 3D network. Then, the
hydrogels were taken out and immersed in 2 mol L
1 H2SO4 to
catalyze the condensation of SiO32
. Further, the composite gels
with IPN structure were washed thoroughly with deionized

ref. 22 that inorganic nanoparticles absorbed on the matrix
network form an isotropic network. Under the connement
eect of the robust three-dimensional (3D) BC matrix, the
composite aerogels (CAs) can withstand the safer and cheaper
freeze drying process, which always causes the fragile solid
inorganic aerogels to crack into small fragments or even
powders, to obtain monolithic silica aerogels. Hence, the tradi-
tional supercritical drying method, which is expensive and
dangerous, could be substituted. Because the microcracks
caused from the crystallization of the uid within the SiO2 gel
skeleton could provide enough space to endure a certain defor-
mation, CAs exhibited remarkable exibility. However, this
method, which needs the freeze drying process twice to
construct the dried BC matrix and CAs, respectively, is involved
and time-consuming. In this work, we ameliorate the synthesis
process and obtain BCsilica CAs with freeze drying only once.
Especially, the precursor used here is sodium silicate (Na2SiO3)
instead of TEOS. Hence, the cost could be largely reduced, and
the synthesis process is more environmentally-friendly.
Furthermore, the hydrophobization modied CAs show stronger
water. Aer solvent exchanged with the mixture of deionized
water and tert-butanol, the wet gels were dried with a freeze
drying method to obtain CAs. CAs were prepared from diusing
the precursor into the wet matrix (i.e. BC hydrogel) followed by
catalyzing the condensation of precursor. It is dierent from our
previous work, diusing the silica alcosols into the dried BC
matrix (i.e. BC aerogel) to continue the solgel process inside of
the BC matrix. This amelioration simplies the preparation
method obviously and promotes the application of aerogels.
Experimental
Materials
The food Nata-de-coco (i.e. BC hydrogel) was procured from
Kuangquan Food Co., Ltd. (Tangshan, China). Sodium silicate
(Na2SiO3$9H2O, molar ratio SiO2 : Na2O 1 : 1) and tert-butanol
were produced by Tianjin Fuchen Chemical Reagents Factory
(Tianjin, China). Sulfuric acid (H2SO4), oxalic acid (C2H2O4) and
ammonia (NH3$H2O) was bought from Beijing Chemical Reagents
Co. (Beijing, China). Methyltrimethoxysilane (MTMS) was

Fig. 1 Schematic illustration of the formation mechanism of CAs. (a) SEM (scanning electron microscopy) image and photograph of BC
hydrogels 3D network (matrix). (b) SEM image and photograph of BCsilica CAs (SiO2 about 95.9% w/w). Firstly, the Na2SiO3 diused into the BC
hydrogel 3D network. Then, the SiO32
converted into SiO2 nanoparticles (represented by blue balls) as H+ diused into the BC 3D network, and
these nanoparticles assembled with the silica gel skeleton to form the IPN structure with the BC network. Lastly, the wet gels were dried with a
freeze drying method to obtain the CAs.

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purchased from Shanghai Jingchun Reagents Co., Ltd. (Shanghai,
China). All reagents were used without further purication.
Preparation of BC matrix
BC matrix was prepared from delicious Nata-de-coco (i.e.
unpuried BC hydrogels). The unpuried BC hydrogels were
immersed in deionized water (4 h) to wash the sugar out. The
washed BC hydrogels were heated to 90  C in a concentrated
NaOH solution (6 h). Then the hydrogels were put in a beaker
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adequately modied by the sol prepared from MTMS. Aer
solvent exchanged with tert-butanol, the wet gels were freeze
dried to obtain hydrophobic CAs.
Characterization
Nitrogen physisorption measurements at 77 K were performed
by a Gemini V, Micromeritics (U.S.A.). The BrunauerEmmett
Teller (BET) analysis from the amount of N2 adsorbed at various
relative vapor pressures (six points 0.05 < p/po < 0.3, nitrogen

with 100 mL water, and the water was stirred with a magnetic
stirrer. The water was changed every 2 hours. Aer 10 hours, the
water was poured o to obtain the semitransparent BC matrix
(Fig. 1a).
Preparation of silicaBC composite gels
The puried BC matrix (i.e. BC hydrogels) was immersed in
dierent concentrations of Na2SiO3 solution (Table 1) at 80  C,
stirred for 8 h to make the precursor diuse into the matrix.
Then, the gels were taken out and immersed in 2 M H2SO4 for
the condensation of SiO32
in the BC matrix for 8 h at ambient
temperature. The resulting composite gels were immersed in
deionized water to wash the residual H2SO4 and the generated
Na2SO4 out from the mesopores of the composite gels.
Freeze drying of silicaBC composite gels
The obtained composite gels were solvent exchanged with a
mixture of deionized water and tert-butanol. Then, the gels were
precooled for 12 h at
20  C, followed by freeze drying for 20 h
to obtain the dried silicaBC composite aerogels (CAs, Fig. 1b).
Hydrophobization modication of the composite aerogels
(CAs)
First, the silica sol was prepared from methyltrimethoxysilane
(MTMS).10 MTMS (1.44 mL), methanol (5 mL) and oxalic acid
(0.01 mol L
1, 0.72 mL) were mixed, stirred for 1 h. Aer 24 h, 10
M ammonia was added to the system, followed by immersion of
the dried silicaBC CAs, stirred for 30 min. The wet gels were
taken out from the system, then aged at room temperature
(24 h) to make sure the silicaBC aerogel skeleton was
molecular cross-sectional area 0.162 nm2) was used to
determine the surface area. The BarrettJoynerHalenda (BJH)
analyses were conducted from the adsorption isotherm when
the pore-size distribution was investigated. Field-emission
scanning electron microscopic (SEM) characterization of the BC
matrix and CAs was performed by a Hitachi S-4800 (Japan).
Thermogravimetric analysis of the BC matrix was carried out by
a NETZSCH STA 449C. The sample was placed in a platinum
pan and heated from 25 to 550  C at a rate of 10 K min
1 under a
nitrogen atmosphere. The X-ray diractometry of the cellulose
and cellulosesilica aerogels was performed by a MSAL-XD2 X-
ray diractometer with Ni-ltered Cu Ka radiation (l 0.1541
nm) in the range of 545 (2q) at 30 kV and 30 mA. Thermal
conductivity of the BC matrix and CAs was measured by a C-
Therm TCi thermal conductivity analyzer (Canada) through a
transient plate method. All the samples were cut to 5 mm
thickness and put on the transient plane source, then a weight
was put on the sample to make sure the contact between the
sample and the transient plane was complete. The stressstrain
curves and the compression modulus were measured by Istron-
3365 exural strength testing systems (America) when all the
samples were carefully cut into similar cuboid forms by sharp
Gillette razors (Super Gillette Blue Blades, China). The contact
angle of CAs with hydrophobization treatment was measured by
a contact angle measuring system (JC2000C1, POWEREACH).
Bulk densities of the matrix and CAs were calculated by
weighing the samples and measuring the volumes. The content
of silica in CAs was calculated from the equation,
 
r
r0
Mass fraction % us  100%
r

Table 1 The properties of CAs prepared with dierent concentration of Na2SiO3 solution

Na2SiO3 solution SiO2 in Bulk density Surface area Thermal cond. Compression
# (% wt) aerogels (% w/w) (g cm
3) (m2 g
1) Porositya (%) (mW m
1 k
1) modulus (MPa)

0b 0 0 0.007 129.0 99.6 29.5 0.27

1 2.5 36.4 0.011 268.5 99.4 30.8 0.38
2 5 69.5 0.023 479.5 98.8 31.5 0.52
3 10 75.3 0.053 541.1 97.3 32.3 1.09
4 15 86.8 0.083 534.5 95.9 33.2 2.17
5 20 93.7 0.111 510.2 94.6 34.0 3.70
6 25 95.1 0.142 390.5 93.2 34.7 6.42
7 30 95.9 0.170 386.9 91.8 35.5 9.33
8 35 96.5 0.199 315.7 90.4 36.2 12.14
9 40 96.9 0.229 288.5 89.0 36.9 16.67
a
The porosity includes the void space caused by crystal growth among the gel skeleton when the gels were frozen. b The pure BC matrix that was
prepared from puried BC hydrogels directly via freeze drying.

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where r and r0 were the bulk density of the CAs and pure BC
matrix, respectively. The porosity of the matrix and CAs was
calculated according to the equation,
 
r
Porosity% 1
 100%
us rs uc rc
where r, rs and rc are the bulk density of CAs, the skeletal
density of the pure silica aerogels and the skeletal density of the
pure BC matrix, respectively; us and uc are the mass fractions of
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silica and BC in the composite aerogels, respectively.22 Herein,
rs and rc were designed to be 2.1 g cm
3 and 1.59 g cm
3.23,24
Results and discussion
Tentative research of the permeation solgel process
The gel time of sodium silicate is determined by the pH of
sodium silicate, and the gel will form instantaneously if the pH
of the solution is adjusted to a suitable range.25,26 It was found
that the clear sodium silicate solution (Fig. 2a) would be con-
verted into milky gels (Fig. 2b) as soon as a certain amount of 2
M H2SO4 was added. In this process, the pH value of this system
was reduced from over 14 to about 10 by the acid catalyst. This
gelation process was completed in a very short time (less than 2
seconds) aer the acid was added, which means the precursor is
Fig. 2 (a) 5 mL Na2SiO3 solution. (b) SiO2 gels that were prepared from
(a). (c) The photo of BC matrix with silica Na2SiO3 solution. (d) and (e)
are the photos of the samples that were obtained by immersing the BC
matrix with silica Na2SiO3 solution in 2 M H2SO4 for 5 min and 8 h,
respectively.
30456 | RSC Adv., 2014, 4, 3045330461
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quite sensitive to the catalyst. It is clearly dierent from the
process of preparing silica gels with organic precursor (e.g.
TEOS), which oen needs several minutes or even a few hours to
complete the solgel process. Hence, we call this gelation of
sodium silicate solution rapid solgel process in this paper.
Based on the rapid solgel process of sodium silica, we sug-
gested a method to construct the IPN structure of BC network
and silica gel skeleton, that is, diusing the acidic catalyst
gradually into the BC matrix, which contained Na2SiO3 solution
to promote the formation of silica gel skeleton in the BC
network. The solgel process would occur if the pH value of the
Na2SiO3 solution in the BC matrix reduced to a suitable range. It
was found that the edges of the semitransparent BC matrix
(Fig. 2c) became milky and lost transmittance when it was
immersed in 2 M H2SO4 for 5 minutes, but the centre of the
simple was still semitransparent and as so as the initial BC
matrix (Fig. 2d). Then, when it was immersed in deionized water
for 30 minutes, the water become alkaline (pH > 11). This could
be understood because the diusion of acid was a slow process,
and the gelation rate of the Na2SiO3 solution in BC matrix was
restricted by the diusion of H+. Hence, although the precursor
is quite sensitive to the acid catalyst, the BC matrix with Na2SiO3
solution should be immersed in the acidic solution for enough
time for sucient diusion of H+. Hence, when it was immersed
in 2 M H2SO4 for 8 h, the whole BC matrix became milky and lost
transmittance (Fig. 2e), and the sample became harder as the
Na2SiO3 solution in the BC matrix converted into a rigid SiO2 gel
skeleton. Then, when it was immersed in the deionized water for
30 minutes, the water become acidic (pH  1). This means that
the acid has thoroughly diused into the matrix, and the system
was changed from strongly alkaline to strongly acidic. In the
process, the Na2SiO3 solution in the BC matrix will meet suitable
conditions to accomplish the solgel when the pH value
decreased to the right range. Aer the solgel process was
accomplished on the periphery of the sample, the H+ would
continually diuse through the SiO2 gel to the inside of the BC
matrix to promote the solgel process in the interior of the BC
matrix. Hence, it is vital to oer enough time to make sure the H+
has thoroughly diused into the BC matrix. In addition, it could
be speculated that the gelation process of Na2SiO3 was carried
out from the outside to the inside of the BC matrix until all the
precursor was converted into SiO2 gel skeleton. This process was
not only dierent from the Na2SiO3 solution, which could induce
the rapid solgel process in the whole solution simultaneously,
but also dierent from the process that constructed the INP
structure with TEOS precursor in our previous work.21 The
distinctive process in this paper could be called a permeation
solgel process. Then, the INP structure of BC network and SiO2
gel skeleton has formed. Aer freeze drying of the silicaBC
composite gels, CAs with INP structure were obtained.
Excellent properties and microstructure of bacterial cellulose
(BC)silica composite aerogels (CAs)
It is found that the CAs could withstand freeze drying to keep
their integrity (the photograph in Fig. 1b). Generally, the solvent
(i.e. water) in the SiO2 hydrogels will crystallize when the
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hydrogels are precooled. The expansion caused from the crys-

tallization process will destroy the integrity of the sti SiO2 gel
skeleton. Consequently, the preparation of intact silica aerogels
with freeze drying used to be a huge challenge.27,28 This problem
has been solved by constructing the IPN of BC and SiO2 gel
skeleton.21 In this work, we constructed the similar IPN struc-
ture (the SEM image in Fig. 1b) of BC and SiO2 gel skeletons
through a dierent way. The similar IPN structure may endow
them with similar properties, e.g. integrity and mechanical
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properties. Although some narrow cracks of silica gel skeleton

can be found in CAs, the silica agglomerations with aerogel
structure were restricted in certain locations by the 3D BC
network to join them together instead of separating each other.
The excellent mechanical properties of BC nanobers (Young's
modulus and tensile strength of individual cellulose nanobers
are almost close to those of steel29,30) played an important role in Fig. 3 (a) Nitrogen adsorptiondesorption isotherms of the CAs (#1 to
the connement eect to guarantee the integrity of CAs. #9). (b) The relevant BJH pore-size distribution calculated from the
Moreover, the BC matrix used as reinforcement was not just the adsorption branch of the nitrogen adsorption and desorption
dispersed individual nanobers, but had a 3D web-like isotherms. The most probable values of pore size were linked by a
morphology. The joints between BC nanobers were solidly black solid line to highlight the variation tendency of the pore size. It is
necessary to illustrate that the curves have been shifted along the Y
xed by large numbers of hydrogen-bonds, which were bene- axis to show these curves clearly.
cial for playing the connement eect of BC matrix. Further-
more, the microcracks caused from the crystallization of the
uid within the SiO2 gel skeleton endow CAs with exibility so
agglomerations were formed under the pressure caused from
that CAs could maintain their integrity even when compressed
the crystallization process of the liquid within the gel skeleton.
about 50% (Fig. S1, ESI), because these microcracks could
The SiO2 gel skeleton was crushed into laminations, because it
provide enough space to allow deformation, and the conne-
was prepared from Na2SiO3 with low concentration, which
ment eect of the robust 3D BC matrix guarantees the integrity
made the gel skeleton rather weak. On the contrary, CAs (#7)
of CAs. This mechanism has been discussed in detail in our
prepared from high concentration (30%) of Na2SiO3 exhibited a
previous work.21
continuous SiO2 aerogel structure instead of discrete, loose SiO2
To investigate the pore character of the obtained CAs, N2
laminations (Fig. 4c and d). Compared with the samples (e.g. #3)
adsorptiondesorption isotherms of the samples (#1 to #9) were
prepared from Na2SiO3 with low concentration, more silica
measured (Fig. 3a). The isotherms gradually showed typical
nanoparticles and more connecting points between the nano-
hysteresis loops as the content of silica increased, which means
particles are formed in the same space. Consequently, the silica
the mesopores could eectively form with high concentration of
gel skeleton is stronger to withstand the pressure caused from
precursor. However, sample #9 prepared from 40% Na2SiO3 did
the crystallization process. Furthermore, the network of nano-
not show the typical hysteresis loops. This phenomenon is
bers were inlaid in the silica gel skeleton to form the IPN
understood as the pore size signicantly decreased because the
structure more eectively (Fig. 4d).
much greater SiO2 in CAs compresses the silica gel skeleton and
reduces its porosity. The BarrettJoynerHalenda (BJH) analyses
were conducted from the adsorption isotherm (Fig. 3b). The
BJH pore-size distribution also shows the character that the
most probable value of pore size increased from 3 nm (#1) to 11
nm (#6) with an increase of the concentration of Na2SiO3, while
the value gradually decreased to 3 nm (#9) with much higher
concentration of the precursor. These phenomena indicate that
the concentration of Na2SiO3 has a remarkable eect on the
pore structure of CAs, and it is essential to control the level of
precursor to obtain the most suitable microstructure.
The SEM images of samples were obtained to conrm how
the concentration of precursor inuenced the microstructure of
CAs. CAs (#3) prepared from Na2SiO3 with low concentration
(10%) exhibited a loose lamellar structure with dierent size
adhered to the BC nanobers, and there was no continuity
between these laminations (Fig. 4a and b). Actually, the akes
were the SiO2 aerogel agglomerations, which were composed of Fig. 4 SEM images: (a) and (b) are CAs based on 10% (wt) Na2SiO3
silica nanoparticles (Fig. 4b). The lamellar SiO2 aerogel solution. (c) and (d) are CAs based on 30% (wt) Na2SiO3 solution.

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The XRD analysis of the obtained CAs showed that the

diraction peaks of BC were gradually covered up by the broad
silica peak with the increase of silica content in CAs (Fig. 5).
There was no other diraction peak apart from the corre-
sponding peaks of BC and silica. Based on ref. 22, this
phenomenon could be understood as they were just homoge-
neous combinations of BC and silica, and the combination did
not generate new phases or new covalent bonds. Hence, the
interaction between BC nanobers and SiO2 was just hydrogen
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bonds.
Based on above results, it could be speculated that the SiO32

would diuse into BC hydrogels once they were immersed into
the Na2SiO3 solution. Then, SiO32
would convert into SiO2
nanoparticles in the BC network as the H+ gradually diused into
the BC hydrogel. The SiO2 nanoparticles would assemble to form
the silica gel skeleton, and the SiO2 nanoparticles adjacent to the
BC nanobers would form hydrogen bonds with the hydroxyl
groups of BC. Furthermore, the silica gel skeleton and the BC
network construct the IPN structure. Aer freeze drying, the IPN
structure could be conserved eectively when high concentration
of Na2SiO3 was used, or the IPN structure would be destroyed by
the pressure caused from the crystallization process.
The IPN structure not only enabled CAs withstand the freeze
drying to maintain their integrity, but also endowed excellent
mechanical properties to CAs. The compression modulus of
CAs gradually increased from 0.38 MPa (#1) to 16.67 MPa (#9)
upon increasing the ratio of silica (Table 1, and the stressstrain
curves are shown in Fig. 6a). The exible BC matrix was eec-
tively supported by the hard inorganic network to sustain the
compression. Hence, the silica aerogel agglomerations in the
BC matrix can dramatically aect the mechanical properties of Fig. 6 (a) Stressstrain curves of BC matrix (# 0) and BCsilica CAs
CAs. As shown in the stressstrain curves (Fig. 6), the curves of (# 1 to # 9). (b) loglog plot of compression modulus versus bulk
density. The regression coecient is 0.97.
samples (#1 and #2) prepared with the low concentration of
Na2SiO3 nearly coincide with the curve of BC matrix (#0),
because the amount and the volume of silica aerogel agglom-
erations in the BC matrix are too small to support each other Na2SiO3 increased, the curves of these samples (#3, #4, #5 and
when CAs are under external pressure. As the concentration of #6) rapidly raised and clearly separated from each other (Fig. 6).
Under these conditions, the microcracks between silica aerogel
agglomerations were signicantly reduced by the increment of
the amount and the volume of silica aerogel agglomerations,
and the higher concentration of Na2SiO3 made the silica aerogel
skeleton stronger to withstand the external pressure rather than
deform. However, the dierence between the stressstrain
curves of CAs (#7, #8 and #9) reduced gradually when we further
increased the concentration of Na2SiO3 (Fig. 6). This phenom-
enon could be understood as the amount and the volume of
silica aerogel agglomerations are hard to further increase
when the concentration of Na2SiO3 has achieved a high level
($30% wt), and the increased Na2SiO3 was consumed to reduce
the pore size of the silica aerogel (this is in accordance with
Fig. 3). Hence, it is easy to adjust the modulus and the exibility
of CAs in a wide range through modulating the concentration of
Na2SiO3. Furthermore, CAs could keep their integrity and did
not show the true breakpoint under relative high external force
because of the connement eect of the 3D BC network. Based
Fig. 5 X-ray diraction of BC matrix (run 0) and CAs with dierent on the IPN structure, the 3D BC network oers an eective
ratios of silica (#1 to #9). connement to make sure the silica aerogel agglomerates with

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the SiO2 gel structure in a relative stable location rather than
disperse. Consequently, both the SiO2 aerogel agglomeration
and 3D BC network endowed CAs with excellent mechanical
properties.
In addition, the loglog plot of compression modulus versus
the bulk density showed that the slope is just 1.78, lower than
the slope (about 2.54) of traditional pure silica aerogels.31,32
This means the rigidity of CAs increases more slowly as the
density increases, compared with traditional aerogels. This may
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be caused by freeze drying, which introduced microcracks in
CAs in this study. These microcracks between silica aerogel
agglomerations not only provide enough space for deformation,
but also made the silica aerogel agglomerations independent of
each other. Hence, the eect of increasing the total amount of
silica and the resulting increasing number of connecting points
between the silica nanoparticles have been restricted by the
microcracks.
CAs exhibited extremely low thermal conductivity, almost
the same as traditional native silica aerogels. The thermal
conductivity increased from 30.8 mW m
1 k
1 to 36.9 mW m
1
k
1 moderately when the content (mass fraction) of silica
increased from 36.4% to 96.9% (Table 1). Consequently, the
narrow microcracks and the IPN structure did not destroy the
excellent adiabatic performance of CAs. In addition, thermog-
ravimetric analysis curves showed that the temperature of
decomposition of the cellulose (BC network) gradually shied
from about 250  C to about 330  C (Fig. 7) as the silica content
increased. For example, the #2 lost 5% of its weight at 320  C,
lost 10% of its weight at 360  C and completely degraded at
about 410  C, while the BC matrix (#0) lost 5% of its weight just
at 265  C, lost 10% of its weight at 290  C and completely
degraded at about 380  C. This dierence could be understood
as the silica had a stabilizing eect on polymer cellulose.22
Hence, CAs can be used at higher temperatures than many
common polymers.
Fig. 7 Thermogravimetric analysis (TGA, 10  C min
1 heating) curves
of BC matrix (# 0) and CAs (# 1 to # 9). It is noted that the Y-axis is the
BC weight (the pure BC matrix and the BC in CAs), but not the weight
of the CAs. Another TGA gure (Y-axis is the weight of the relative
sample, not just the BC weight) could be seen in Fig. S2 ESI.
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RSC Advances
Hydrophobization modication of composite aerogels (CAs)
Unlike traditional pure silica aerogels, it was found that the
dried CAs could maintain their integrity even when immersed
into liquid again (Fig. 8a). In addition, the microstructure of
CAs did not show obvious change when they were freeze dried
again (Fig. S3, ESI). The IPN structure that had been intro-
duced in CAs was benecial for withstanding the huge capillary
force. Moreover, the micron-size silica aerogel agglomerations
could easily deform together with the BC nanobers to
accommodate the pressure caused from the meniscus during
the wetting process. Besides, the connement eect of the
robust 3D BC matrix played an important role to prevent the
silica aerogel agglomerations separating from each other and
dispersing in the liquid when dried CAs were immersed into
liquid again.21
In addition, it was found that CAs absorbed water and sank
into the bottom of the water quickly (less than 10 s) when we put
CAs on the water. The excellent absorption property indicated
that CAs could be further functionalized in liquid with a
hydrophobic modication agent to extend their applications.
The CAs (#7) were immersed in the sol prepared from methyl-
trimethoxysilane (MTMS) followed by freeze drying to accom-
plish the hydrophobization modication. The modied CAs
could oat on the water surface (Fig. 8b) because of their
hydrophobic property (the contact angle is about 145 ) and low
density (0.219 g cm
3). Compared with our previous work, the
contact angle of the hydrophobic CAs increased from 133 to
145 . This obvious increment could be explained by Wenzel's
theory that the liquid follows the roughness of the surface.3335
At thermodynamic equilibrium, the apparent contact angle of
the sample surface and the roughness factor of the given surface
have the relationship:
cos qw r cos q
where qw corresponds to the apparent contact angle, r repre-
sents the roughness factor, and q refers to Young's angle. In this
work, the method and the agent of hydrophobization modi-
cation were same as in our previous work. Hence, the Young's
angle q of the corresponding sample surface is the same. Then,
the higher apparent contact angle means that the roughness
factor r has increased. The dierence of the roughness factor r
could be understood as the silica gel skeleton formed through a
Fig. 8 (a) Exhibition of CAs being wetted again (sink in the water). (b)
The hydrophobic CAs oating on water.
RSC Adv., 2014, 4, 3045330461 | 30459

RSC Advances
dierent process. The solgel process was carried out under
mild reaction conditions (the dilute acid catalyst and the dilute
alkaline catalyst were carefully controlled to make the solgel
process proceed gently in nearly neutral conditions) in our
previous work. However, in this work, the BC matrix with
Na2SiO3 solution was immersed in 2 mol L
1 H2SO4 (pH < 1).
The SiO32
rapidly converted into silica nanoparticles, and
silica nanoparticles assembled into silica gel skeleton.
Compared with the mild solgel process in our previous work,
Published on 18 June 2014. Downloaded by Universitaet Duisburg Essen on 10/04/2017 10:24:06.
this permeation solgel process made the silica nanoparticles'
surface more heterogeneous. Then, the roughness of the
sample surface and the relative roughness factor r eectively
increased. Hence, the apparent contact angle of the sample
increased obviously.
Aer hydrophobization modication, the micromorphology
of CAs did not change obviously (Fig. S4, ESI) except that the
silica nanoparticles became bigger, and they also showed a
large specic surface area (324.5 m2 g
1). Hence, the hydro-
phobic CAs presented excellent oil absorption capability on the
water surface (Fig. 9). The hydrophobic CAs can keep their
integrity aer absorbing oil and could be removed from the
water surface easily, whereas for pure silica aerogels that had
absorbed oil, it was dicult to separate the absorbent with oil
from the water because the brittle aerogels could not endure the
capillary force and cracked seriously when oils were absorbed in
the mesopores of the aerogels.36 Interestingly, it was found that
the hydrophobic CAs with oil could be conveniently washed by
immersing them in an organic solvent (e.g. alcohol) (Fig. 9), and
the washed hydrophobic CAs were reusable aer freeze drying.
Consequently, CAs are benecial for use as an ideal recyclable
material to clean oil spills in a marine environment.
Fig. 9 The contact angle of hydrophobic CAs is about 145 , and the
photos show the oil absorption capability of the hydrophobic CAs.
Herein, 17 mg hydrophobic CAs were placed on the water surface with
150 mL vegetable oil colored with a red dye. Then, the hydrophobic
CAs with oil could be washed by alcohol to achieve recycling.
30460 | RSC Adv., 2014, 4, 3045330461
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Paper
Conclusions
A method to prepare BCsilica CAs with IPN structure has been
proposed. Besides excellent mechanical properties, the
obtained CAs showed low density, high surface area and low
thermal conductivity. Compared with previous methods to
construct the IPN of BC matrix and silica aerogel skeleton, the
times of freeze drying process has reduced from twice to once to
obtain CAs. The eciency of producing the BCsilica CAs has
risen greatly. Furthermore, the precursor used here is sodium
silicate instead of TEOS. This improvement not only reduced
the cost, but also made the synthesis process more environ-
mentally-friendly. In addition, because the roughness of the
sample surface was enhanced by the permeation solgel
process, the corresponding contact angle increased from 133
to about 145 aer the same hydrophobization modication.
The outstanding hydrophobicity and the large specic surface
area endowed the hydrophobic CAs with excellent oil absorp-
tion capability on the water surface. What is more interesting is
that the hydrophobic CAs with oil could be washed and recy-
cled. In conclusion, the new method to prepare CAs with
excellent properties by a non-supercritical drying process is
benecial for promoting the utilization of aerogels.
Acknowledgements
This work was supported by the National Basic Research
Program of China (973 Program) with no. 2011CB706900, the
National Nature Science Foundation of China (no. 50872149
and 50502003), the Scientic Research Foundation for Returned
Scholars within the Ministry of Education of China, and the
President Foundation of the Graduate University of the Chinese
Academy of Sciences.
Notes and references
1 N. H using and U. Schubert, Angew. Chem., Int. Ed., 1998, 37,
2245.
2 A. C. Pierre and G. M. Pajonk, Chem. Rev., 2002, 102, 4243
4266.
3 L. Martin, J. O. Osso, S. Ricart, A. Roig, O. Garcia and
R. Sastre, J. Mater. Chem., 2008, 18, 207213.
4 D. J. Boday, P. Y. Keng, B. Muriithi, J. Pyun and D. A. Loy, J.
Mater. Chem., 2010, 20, 68636865.
5 J. Fricke, J. Non-Cryst. Solids, 1988, 100, 169173.
6 J. Grob and J. Fricke, Nanostruct. Mater., 1995, 6, 905908.
7 G. Reichenauer, J. Non-Cryst. Solids, 2004, 350, 189195.
8 R. A. Strm, Y. Masmoudi, A. Rigacci, G. Petermann,
L. Gullberg, B. Chevalier and M. A. Einarsrud, J. Sol-Gel Sci.
Technol., 2007, 41, 291298.
9 F. He, H. Zhao, X. Qu, C. Zhang and W. Qiu, J. Mater. Process.
Technol., 2009, 209, 16211626.
10 A. V. Rao, S. D. Bhagat, H. Hirashima and G. M. Pajonk, J.
Colloid Interface Sci., 2006, 300, 279285.
11 D. Y. Nadargi, S. S. Latthe, H. Hirashima and A. V. Rao,
Microporous Mesoporous Mater., 2009, 117, 617626.
This journal is The Royal Society of Chemistry 2014

Paper
12 K. Kanamori, M. Aizawa, K. Nakanishi and T. Hanada, Adv.
Mater., 2007, 19, 15891593.
13 S. J. Kramer, F. RubioAlonso and J. D. MacKenzie, Mater. Res.
Soc. Symp. Proc., 1996, 435, 295300.
14 B. M. Novak, D. Auerbach and C. Verrier, Chem. Mater., 1994,
6, 282286.
15 M. A. B. Meador, C. M. Scherzer, S. L. Vivod, D. Quade and
B. N. Nguyen, ACS Appl. Mater. Interfaces, 2010, 2, 21622168.
16 M. A. B. Meador, A. S. Weber, A. Hindi, M. Naumenko,
Published on 18 June 2014. Downloaded by Universitaet Duisburg Essen on 10/04/2017 10:24:06.
L. McCorkle, D. Quade, S. L. Vivod, G. L. Gould, S. White
and K. Deshpande, ACS Appl. Mater. Interfaces, 2009, 1,
894906.
17 M. A. B. Meador, L. A. Capadona, L. McCorkle,
D. S. Papadopoulos and N. Leventis, Chem. Mater., 2007,
19, 22472260.
18 M. A. B. Meador, E. F. Fabrizio, F. Ilhan, A. Dass,
G. H. Zhang, P. Vassilaras, J. C. Johnston and N. Leventis,
Chem. Mater., 2005, 17, 10851098.
19 B. N. Nguyen, M. A. B. Meador, M. E. Tousley, B. Shonkwiler,
L. McCorkle, D. A. Scheiman and A. Palczer, ACS Appl. Mater.
Interfaces, 2009, 1, 621630.
20 J. P. Randall, M. A. B. Meador and S. C. Jana, ACS Appl. Mater.
Interfaces, 2011, 3, 613626.
21 H. Sai, L. Xing, J. Xiang, L. Cui, J. Jiao, C. Zhao, Z. Li and F. Li,
J. Mater. Chem. A, 2013, 1, 79637970.
22 J. Cai, S. Liu, J. Feng, S. Kimura, M. Wada, S. Kuga and
L. Zhang, Angew. Chem., Int. Ed., 2012, 51, 20762079.
This journal is The Royal Society of Chemistry 2014
View Article Online
RSC Advances
23 N. H using, U. Schubert, R. Mezei, P. Fratzl, B. Riegel,
W. Kiefer, D. Kohler and W. Mader, Chem. Mater., 1999,
11, 451457.
24 L. Heath and W. Thielemans, Green Chem., 2010, 12, 1448
1453.
25 R. C. Merrill and R. W. Spencer, J. Phys. Colloid Chem., 1950,
54, 806812.
26 K. S. W. Sing and J. D. Madeley, J. Appl. Chem., 1953, 3, 549
556.
27 A. Bisson, A. Rigacci, D. Lecomte, E. Rodier and P. Achard,
Drying Technol., 2003, 21, 593628.
28 J. L. Gurav, I.-K. Jung, H.-H. Park, E. S. Kang and
D. Y. Nadargi, J. Nanomater., 2010, 2010, 111.
29 H. Yano, J. Sugiyama, A. N. Nakagaito, M. Nogi, T. Matsuura,
M. Hikita and K. Handa, Adv. Mater., 2005, 17, 153155.
30 S. Iwamoto, W. Kai, A. Isogai and T. Iwata,
Biomacromolecules, 2009, 10, 25712576.
31 J. Grob and J. Fricke, Nanostruct. Mater., 1995, 6, 905908.
32 T. Woignier, J. Reynes, A. H. Alaoui, I. Beurroies and
J. Phalippou, J. Non-Cryst. Solids, 1998, 241, 4552.
33 X. M. Li, D. Reinhoudt and M. Crego-Calama, Chem. Soc.
Rev., 2007, 36, 13501368.
34 R. N. Wenzel, Ind. Eng. Chem., 1936, 28, 988994.
35 M. Miwa, A. Nakajima, A. Fujishima, K. Hashimoto and
T. Watanabe, Langmuir, 2000, 16, 57545760.
36 J. L. Gurav, A. V. Rao, D. Y. Nadargi and H.-H. Park, J. Mater.
Sci., 2010, 45, 503510.
RSC Adv., 2014, 4, 3045330461 | 30461