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Aerogels from nanofibrillated cellulose with tunable oleophobicity

Christian Aulin,ab Julia Netrval,b Lars W
agberg*b and Tom Lindstr€omc
Received 28th January 2010, Accepted 19th April 2010
First published as an Advance Article on the web 14th May 2010
DOI: 10.1039/c001939a

The formation of structured porous aerogels of nanofibrillated cellulose (NFC) by freeze-drying has
been demonstrated. The aerogels have a high porosity, as shown by FE-SEM and nitrogen adsorption/
desorption measurements, and a very low density (<0.03 g cm3). The density and surface texture of the
aerogels can be tuned by selecting the concentration of the NFC dispersions before freeze-drying.
Chemical vapor deposition (CVD) of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFOTS) was used
Published on 14 May 2010 on http://pubs.rsc.org | doi:10.1039/C001939A

to uniformly coat the aerogel to tune their wetting properties towards non-polar liquids. An XPS
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analysis of the chemical composition of the PFOTS-modified aerogels demonstrated the reproducibility
of the PFOTS-coating and the high atomic fluorine concentration (ca. 51%) in the surfaces. The
modified aerogels formed a robust composite interface with high apparent contact angles (q* [ 90 )
for castor oil (glv ¼ 35.8 mN m1) and hexadecane (glv ¼ 27.5 mN m1).

Introduction abundant renewable natural polymers, widely used in industry.

Aerogels are materials prepared by replacing the liquid solvent in
a gel by air without substantially altering the network structure or
the volume of the gel body.1 The first aerogels were reported by
Kistler in 1931–1932,2,3 but active research in this area did not
start until about 40 years later. Some of the unique properties of
aerogels are their low density, high specific surface area, low
thermal conductivity and low dielectric permittivity. The prepa-
ration, physical properties and applications of aerogels are
described elsewhere.4,5 The liquid in a wet gel is usually replaced
with air by using supercritical drying, but ambient-pressure
drying has also been attempted.4,6 From a practical point of view,
the challenge has been to prepare aerogels without supercritical
drying in order to reduce the cost. An alternative can be freeze-
drying7–9 where the solvent in the gel is first frozen and then
sublimated without entering the liquid state. The most common
aerogels are inorganic, prepared by sol–gel polymerization of
inorganic metal oxides.10–14 They are usually very brittle, but have
a high compressive strength. Various types of organic aerogels
have also been presented.15–17 Resorcinol/formaldehyde (RF) and
melamine/formaldehyde (MF) are two of the most common
precursor mixtures for forming the organic network.17–19
In the context of a sustainable society, there is strong moti-
vation to replace petroleum-based polymers with polymers from
renewable resources. Porous materials with nano- and micro-
sized pores made from natural polymers are of special interest for
medical, cosmetic, pharmaceutical, and other applications where
biocompatibility and biodegradability are required.20–22 Three-
dimensional scaffolds for tissue engineering, delivery matrices,
‘‘green’’ packaging, and environment-friendly insulating mate-
rials are examples of such applications. Among the poly-
saccharides, cellulose has a special potential as one of the most
a
BIM Kemi AB, Box 3102, SE-443 03 Stenkullen, Sweden
b
Department of Fibre and Polymer Technology, School of Chemical
Science and Engineering, The Royal Institute of Technology, SE-100 44
Stockholm, Sweden. E-mail: wagberg@kth.se
c
Innventia AB, Box 5604, SE-114 86 Stockholm, Sweden
In plant cellulose, the polysaccharide chains with b-(1–4)-D-glu-
copyranose repeating units pack into long fibrils with cross-
sectional dimension of ca. 5–30 nm, depending on the plant
source.23 The high modulus and high strength of native cellulose
I are results of the organization of the cellulose chains in a crystal
structure in which the long parallel polysaccharide chains are
physically bonded together by a large number of hydrogen bonds
and are organized in sheets packed in a ‘‘parallel-up’’ fashion.24 It
is interesting and challenging to consider the long nanofibers as
construction units for nanoscale material engineering.
The term ‘‘nanofibrillated cellulose’’ (NFC) refers to cellulosic
I fibrils disintegrated from the plant cell walls. The preparation of
NFC derived from wood, and specification of the term, were first
described by Turbak et al.25 and Herrick et al.26 more than two
decades ago. Through a homogenization process, wood pulp is
disintegrated, to give a material in which the fibres are degraded
and opened into their sub-structural units. New methods for the
manufacture of smaller and more homogeneous nanofibrillated
cellulose (NFC) have recently been developed and offer new
attractive concepts for material science and significantly enhance
the applicability of cellulose in novel applications.27–30 Recently,
NFC was prepared by a combination of mechanical and enzy-
matic pretreatment followed by high-pressure homogenization31
or by high-pressure homogenization of carboxymethylated
cellulose fibers followed by ultrasonication and centrifugation.32
The latter carboxymethylation pretreatment makes the fibrils
highly charged and easier to liberate, and this results in slightly
smaller and more uniform fibril dimensions than in the enzyme-
treated NFC.33 Since the fibrils are 5–20 nm thick and have
a length of up to several mm, they can be regarded as nanofibres.
Cellulose nanofibrils show very interesting properties as rein-
forcement elements in polymer nanocomposites,34–36 but
a surface modification of the nanofibrils might further widen the
applications since they can be incorporated into new bio-based
materials with a tuned interaction potential. In this respect,
a hydrophobation of the aerogels is a very interesting research
area.

3298 | Soft Matter, 2010, 6, 3298–3305 This journal is ª The Royal Society of Chemistry 2010

The need for surface hydrophobicity has become a hot
research topic which has stimulated a rich variety of studies
describing different approaches for material engineering.37–41
Several studies have also been conducted on the chemical
modification/hydrophobation of nanocellulose.30,42,43 The most
effective treatments use chemical or physical means to append
fluorinated moieties which induce both hydrophobic and oleo-
phobic properties to the resulting low-energy surfaces. The
presence of these moieties also tends to impart a high thermal
stability and reduce chemical and biological fragility.
It is highly desirable for superhydrophobic surfaces also to be
oil-repellent in order to maintain their superhydrophobicity. For
instance, in an industrial or household environment, a super-
hydrophobic surface with poor oil repellency can easily be
Published on 14 May 2010 on http://pubs.rsc.org | doi:10.1039/C001939A
contaminated by oily substances, and this will compromise the
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superhydrophobicity of the surface. Therefore, superoleophobic
surfaces combining both superhydrophobic and superoleophobic
properties are desirable for many practical applications.44,45
Modifying the cellulose aerogel network with fluorinated
organic compounds could widen their applications towards self-
cleaning surfaces in a vast array of products, including green
constructions, packaging materials, protection against environ-
mental fouling, sports and outdoor clothing, and microfluidic
systems. The use of cellulose-based materials could thus be
extended to new areas by the introduction of functional moieties
onto the fiber surface.
Despite extensive investigations on superhydrophobic surfaces,
studies on superoleophobic surfaces with high repellency against
liquids with low surface tension (<35 mN m1) have so far been
rather limited. Oil repellency has been examined on various per-
fluorinated, superhydrophobic surfaces.46–48 Very recently, truly
superoleophobic surfaces have been achieved on the basis of
etched silicon surfaces45 with nanonail49 structures, exemplified by
low contact angle hysteresis for probe liquids of low surface
tension (<30 mN m1), such as octane. In both cases, the key to
obtaining true superoleophobicity is the re-entrant or overhang
surface structure, which ensures the entrapment of air beneath the
top solid surface and prevents the transition from the Cassie–
Baxter state to the Wenzel state.45,49,50 However, the fabrication of
most superoleophobic surfaces involves lithography and etching
steps, and this may limit their practical applications.
In the present work, a novel route for the production of
superoleophobic NFC aerogels is used based on aerogel skele-
tons formed by long and entangled cellulose I containing nano-
scopic fibrils. It gives an aerogel with sufficient strength to
oppose its tendency to collapse during the solvent extraction. The
aerogel network was modified with the aid of chemical vapor
deposition of a fluorinated silane. By adjusting the concentration
of the NFC dispersion before freeze-drying, the surface texture of
the aerogels was altered, making it possible to optimize the
degree of oleophobicity.
Experimental
Preparation of NFC aerogels and films
The anionic NFC used in this study was prepared by a proce-
dure similar to that previously described31 but using a carboxy-
methylation32 pretreatment of the fibers. In brief, the
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dissolving pulp (Domsj€ o dissolving plus) was first dispersed in
deionized water at 10 000 revolutions in an ordinary laboratory
reslusher. The fibers were then solvent-exchanged to ethanol by
washing the fibers in ethanol four times with an intermediate
filtration step. The fibers were then impregnated for 30 min with
a solution of 10 grams of monochloroacetic acid in 500 mL of
isopropanol. This carboxymethylation reaction was allowed to
continue for 1 h. Following the carboxymethylation step, the
fibers were filtered and washed in three steps: first with deion-
ized water, then with acetic acid (0.1 M), and finally with
deionized water. The fibers were then impregnated with
a NaHCO3 solution (4 wt% solution) in order to convert the
carboxyl groups to their sodium form to further enhance the
delamination of the fibers into nanofibrils. Finally, the fibers
were washed with deionized water and drained on a B€ uchner
funnel. After this treatment, the fibers were passed through
a high-pressure homogenizer (Microfluidizer M-110EH, Mir-
cofluidics Corp). Cellulose slurries containing a 2 wt% pulp fibre
suspension in deionized water were processed through the
homogenizer. Such a procedure lead to the liberation of cellu-
lose I nanofibers, mostly with cross-sectional diameters of 5–20
nm and lengths of a few micrometres, although some larger
entities were formed. The so prepared NFC is hence a disper-
sion of nanofibers. NFC dispersions with concentrations of ca.
0.003–2.6 wt% were prepared by diluting the 3.13 wt% NFC
dispersion with deionized water followed by mixing (8000 rpm)
using an Ultra Turrax mixer (IKA D125 Basic, Germany) for
5 min. The total charge density of the highly carboxymethylated
NFC dispersions was measured to be 627 meq. g1 (ref. 32) by
conductometric titration.51 The degree of substitution was
measured to be 0.1. The surface charge density, measured by
polyelectrolyte titration52 using poly-DADMAC (Ciba, York-
shire, UK, Mw ¼ 440 000 g mol1 and 3 ¼ 6.19 meq. g1), was
measured to be 426 meq. g1.
Cylindrical PDMS cups (48 mm in diameter, 16 mm in height)
were used as moulds for the preparation of the aerogels. The
aqueous gel was placed in the mould and the mould was plunged
into liquid nitrogen. Thereafter, the frozen sample in the mould
was transferred to a vacuum oven at 52  C (Labconco Free-
Zone 6, US), and the sample was kept frozen during the drying at
a pressure of ca. 0.016 mbar. The drying was typically finished
within 24 h. The density of the aerogels was obtained as the mass
divided by the volume (4.9 cm3) of the samples.
A free-standing film of NFC was prepared by pouring a 0.1
wt% NFC dispersion onto polystyrene Petri dishes with a diam-
eter of 14 cm. The film was allowed to form upon drying at
a temperature of 23  C and a relative humidity (RH) of 50%. The
dried free-standing film was stored in a desiccator prior to
analysis.
Modification by perfluoroalkylsilane
The silane treatment was carried out by chemical vapor deposi-
tion of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFOTS)
(97%, Sigma Aldrich). Samples were placed on a copper grid
located 5 cm above a beaker containing the fluorinated silane,
which was heated at 140  C for one hour. The samples were
stored in a desiccator prior to analysis.
Soft Matter, 2010, 6, 3298–3305 | 3299
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Scanning electron microscopy

To study the micro-structure of the NFC aerogels, the specimens

were studied with a Hitachi S-4800 field emission scanning
electron microscope (FE-SEM) to obtain secondary electron
images. The specimens were fixed on a metal stub with colloidal
graphite paint and coated with a 6 nm thick gold/palladium layer
using a Cressington 208HR High Resolution Sputter Coater.

Nitrogen adsorption/desorption measurements

The specific surface areas were determined by N2 adsorption/

Fig. 1 Example of cylindrically shaped aerogels obtained from freeze-
desorption measurements at the temperature of liquid nitrogen
drying of (a) 0.7 and (b) 1.1 wt% NFC dispersions.
(ASAP 2020, Micromeritics, US). Before measurement, the
samples were dried at a temperature of 117  C until a vacuum of
Published on 14 May 2010 on http://pubs.rsc.org | doi:10.1039/C001939A

<105 mmHg was reached. Both adsorption and desorption demonstrates the macroscopic integrity achieved, as specimens
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isotherms were measured and the surface area was determined
from the adsorption results using the Brunauer–Emmet–Teller
(BET) method.
Contact angle measurements
A CAM 200 (KSV Instruments Ltd, Helsinki, Finland) contact
angle goniometer was used for advancing contact angle
measurements. The software delivered by the instrument manu-
facturer calculates the contact angle on the basis of a numerical
solution of the full Young–Laplace equation. Measurements
were performed at room temperature with two non-polar, low
surface tension probe liquids: castor oil (Sigma Aldrich) and
hexadecane (>99%, anhydrous, Sigma Aldrich). The contact
angle was determined at three different positions on each sample.
The values reported were taken after the contact angle had
reached a stable value, typically less than 10 s after deposition of
the droplet. Typical uncertainties in the experiments were 4 .
X-Ray photoelectron spectroscopy (XPS)
The XPS spectra were collected with a Kratos Axis Ultra DLD
electron spectrometer (UK) using a monochromated Al Ka
source operated at 150 W, with a pass energy of 160 eV for wide
spectra and a pass energy of 20 eV for individual photoelectron
lines. The surface potential was stabilized by the spectrometer
charge neutralization system. Photoelectrons were collected at
a take-off angle of 90 relative to the sample surface and the
depth of analysis was ca. 10 nm. The binding energy (BE) scale
was referenced to the C 1s line of aliphatic carbon, set at 285.0
eV. The spectra were processed with the Kratos software and the
CasaXPS program package including experimental values for the
atomic sensitivity factors, and peak intensities were determined
by integrating the areas under the peaks.
with well-defined shapes were prepared.
The densities of the samples were very low. Fig. 2 shows the
density of the aerogels as a function of the initial NFC dispersion
concentration. The aerogel density was almost linearly propor-
tional to the dispersion concentrations. For example, aerogels
prepared from 0.5 and 3.13 wt% dispersions resulted in material
densities of 0.0053 and 0.030 g cm3, respectively. The aerogel
prepared from the 0.5 wt% dispersion had a very high porosity,
ca. 99.7%, where the porosity F is defined as F ¼ 1  (r/rs),
where r and rs (1.63 g cm3)53 are the densities of the aerogel and
the crystalline Ib cellulose fibril, respectively. For comparison,
the aerogel prepared from the 3.13 wt% dispersion had a porosity
of ca. 98.2%.
The specific surface area was analyzed by N2 adsorption/
desorption at 77 K. Aerogels with densities of 0.030 and 0.020 g
cm3 showed BET specific surface areas of 11 and 15 m2 g1,
respectively. Evidently, the BET-area increased with decreasing
density of the aerogels as expected. These values were lower than
in a previous study by P€ a€
akk€o et al.,20 who reported a value of 66
2 1
m g for low-charged NFC aerogels prepared from a 2 wt%
NFC-dispersion.
As previously shown in detail under aqueous conditions, the
initial ‘‘wet’’ gel, i.e. NFC in water, consists of long and entan-
gled fibrils with diameters of ca. 5 nm with occasional thicker
fibril bundles.31 Fig. 3 presents FE-SEM micrographs showing
the surface texture of aerogels with densities of 0.00027, 0.0018,
0.0053, 0.0070, 0.011 and 0.030 g cm3, respectively. As the

Results
Structural characteristics of NFC aerogels
Aerogels from NFC dispersions of various concentrations
(ranging from 0.0031 wt% to 3.13 wt%) were prepared and their
structural properties were compared. After complete water
removal through freeze-drying, lightweight sponge-like aerogel Fig. 2 Aerogel density (g cm3) as a function of NFC dispersion
was produced which had not significantly collapsed. Fig. 1 concentrations during freeze-drying (g l1).

3300 | Soft Matter, 2010, 6, 3298–3305 This journal is ª The Royal Society of Chemistry 2010

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Fig. 3 Low-magnification (100) FE-SEM micrographs of aerogels
fabricated by the freeze-drying of aqueous NFC dispersions. The densi-
ties of the aerogels are (a) 0.00027 (b) 0.0018 (c) 0.0053 (d) 0.0070 (e)
0.011 and (f) 0.030 g cm3. All images are top-view images and the scale
bars are 500 mm.
density of the aerogels increased, the amount of pores and
protruding sheets decreased. This was accompanied by a gradual
closure of the surface texture. At densities <0.0070 g cm3, the
aerogel typically consisted of an open network of extended thin
sheets forming macroscopic ‘‘open channels’’ and large, several
micrometre wide pores that connect the different cells and
thin sheets of the aerogel. When the density was increased to
Fig. 4 FE-SEM micrographs showing (a) a typical cross-section of
a sheet, (b and c) fibril-aggregates protruding from the cell walls forming
network structures and (d) the fibrillar aerogel skeleton. Scale bars are (a)
40 mm (b) 10 mm (c) 50 mm and (d) 10 mm.
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0.011 g cm3, the number of pores and the pore size decreased
significantly accompanied with the formation of more sheet-like
structures. At a density of 0.030 g cm3, no macroscopic pores
were observed (Fig. 3f). Instead, the aerogel had a much more
closed surface texture with thin sheets exhibiting random
formations of ‘‘wave-like’’ roughness.
The pore and sheet structures of the 0.0070 g cm3 aerogel were
further studied by FE-SEM at higher magnifications, and some
micrographs are presented in Fig. 4. A typical sheet thickness of
about 4–8 mm formed from aggregated nanofibrils is revealed in
Fig. 4a. Nanofibril-aggregates or nanofibril bundles with diam-
eters in the order of 500 nm, are protruding from the surface of
the sheets (Fig. 4b), some of them forming very open networks
(Fig. 4c). These surface features were especially apparent in the
aerogels with densities <0.01 g cm3. Fig. 4d shows an inter-
connected fibrillar structure of long and entangled nanofibril
aggregates with diameters of 100 nm with occasional thicker
bundles. The image reveals that the fibril network has a random-
in-plane orientation.
Surface wettability
It is well established that in order to obtain a thin film coverage
of trichlorosilanes on any substrates, reactive OH-groups on the
surface are generally required.47,54 These OH-groups can react
with functionalized silanes (usually trichlorosilane) in the
gaseous or solvent phase to yield preferably monolayers with
the desired functionality depending on the chemical composi-
tion of the selected silane. In the work, this type of coating was
applied to the structured and flat cellulose surfaces (aerogels
and solvent-cast film, respectively) by simply reacting the
hydroxylic groups of the cellulose with trichlorosilane. The
unique structure of the coating was found to significantly
decrease the wetting properties evaluated by contact angle
measurements using two probe liquids: castor oil and hex-
adecane with surface tensions of 35.8 and 27.5 mN m1,
respectively. However, pure non-modified NFC aerogels and
films were completely wettable (q z 0 ) by castor oil. When
1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS) was
applied in the refunctionalization step, the structured coatings
displayed clear oleophobic properties (q [ 90 ). Fig. 5 shows
the advancing contact angle for castor oil as a function of the
density of the PFOTS-coated aerogels.
Fig. 5 Advancing contact angle for castor oil (glv ¼ 35.8 mN m1) as
a function of the density of the PFOTS-coated aerogels.
Soft Matter, 2010, 6, 3298–3305 | 3301

Fig. 6 Droplets of (a) castor oil and (b) hexadecane on top of a PFOTS-
coated aerogel with a density r ¼ 0.0070 g cm3.
The most oleophobic aerogel (r ¼ 0.0070 g cm3) exhibited
contact angles of roughly 166 and 144 for castor oil and hex-
Published on 14 May 2010 on http://pubs.rsc.org | doi:10.1039/C001939A
adecane respectively (Fig. 6), which, to the knowledge of the
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authors, are among the highest contact angles reported in the
literature for any substrate against liquids or liquids with similar
surface tensions.45,47,50,55 At densities >0.020 g cm3, the
advancing contact angle gradually decreased down to ca. 100 .
At densities below 0.0003 g cm3, the advancing contact angle
decreased down to 0 . Between the aerogels with densities of
0.00035 and 0.00027 g cm3 there is a rapid transition from
a perfectly non-wetting (q [ 90 ) to a completely wetting
surface (q z 0 ). A contact angle denoted 0 indicates that the
surface was not sufficiently robust to support a 10 ml droplet of
castor oil, and that the liquid droplet was rapidly (<10 s) imbibed
into the surface. Transitions from perfectly non-wetting (q [
90 ) to completely wetting surfaces (q z 0 ) between aerogels
with densities of 0.00035 and 0.00027 g cm3 were also observed
for hexadecane and water. As expected, there was a large
difference between the contact angle values on the structured
aerogels and on the smooth solvent-casted NFC film. For
comparison, the contact angles for castor oil and hexadecane on
PFOTS-modified smooth NFC films were 96 and 71 , respec-
tively, demonstrating the necessity of having a highly textured
surface to achieve the high contact angles against low surface
tension liquids.
The XPS analysis revealed the surface chemical composition of
the NFC aerogels and film before and after PFOTS-coating. The
atomic concentrations of the surfaces of pure NFC aerogel and
film and their modified analogues are given in Table 1. Carbon,
oxygen and very small amounts of Na as counterions of the
carboxymethylated cellulose fibrils were detected on the surface
of the cellulose samples, whereas the modified samples clearly
showed also the presence of fluorine and silicon, which supported
that PFOTS had reacted with the cellulose. The total oxygen
concentration decreased from 38.2% to 6.6%, and the fluorine
concentration was found to be 51%. The atomic surface
concentrations of C, O, Si and F were similar for all the
Table 1 Atomic surface concentration on PFOTS-coated and non-
coated NFC aerogels and films
Surface concentration (at%)
C O Na Si
Pure NFC aerogels/film 61.3 38.2 0.6
PFOTS-coated NFC aerogels/film 37.6 6.6 4.8
3302 | Soft Matter, 2010, 6, 3298–3305
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structured PFOTS-coated aerogels and films. As in the case of
the fluorinated NFC aerogels, the fluorine signal from the
PFOTS-coated NFC film was determined to be 51%, indicating
reproducible results from the PFOTS-coating. The pure
NFC aerogel and film showed a lower oxygen to carbon ratio
(O/C-ratio), 0.62, compared with the theoretical value of pure
cellulose, 0.83. Hydrocarbons tend to be the most common
surface contaminant, and it is quite common to see C–H peaks in
cellulose samples.56 Although the aerogels and films were
handled carefully, it is possible that some surface contamination
occurred. The high-surface area of the cellulose nanofibrils
makes it even more difficult to avoid contamination during
e.g. film formation and storage. The uncertainty of the XPS
determinations was within 1%.
Discussion
Preparation of NFC aerogels by freeze-drying
In the present work, highly porous NFC aerogels were prepared
by direct water removal by freeze-drying. The primary aim has
been to clarify the factors controlling the surface properties of
these aerogels and to further modify and tune the oil-wetting/
resistance properties of these materials. The surface texture
rather then the bulk properties of the aerogels was the aspect of
major interest in this study. Nevertheless, as indicated by the
FE-SEM and nitrogen adsorption/desorption-measurements, the
porosity, density and surface morphology can be tuned by
switchable adjustments of the concentration of the NFC
dispersions before freeze-drying. A higher NFC concentration
leads to a lower specific surface area of the aerogel. The same
phenomenon was reported for freeze-dried cellulose/calcium
thiocyanate solutions of different cellulose concentrations57 and
for low-charged NFC aerogels.20 The influence of freeze-drying
conditions on the morphology and porosity of aerogels has been
studied before, e.g. for NFC-based foams,20,22 regenerated
cellulose II57 and for starch-based foams reinforced with NFC.36
The observed specific surface areas of the present aerogels were
lower than those reported for freeze-dried fibrillar cellulose aer-
ogels.20,21 This is probably due to a slower cooling of the NFC
dispersions by the liquid nitrogen than the cooling by liquid
propane used in the work of P€ a€ o et al.20 Rapid cooling is
ak€
known to be accompanied by the formation of amorphous ice
which may lead to a more homogeneous fibrillar structure of the
aerogel with smaller pores and less pronounced sheet-like
structure of the aerogel.58 In contrast, cooling by liquid nitrogen
enhances the formation of non-amorphous ice (crystals) which
contributes to the sheet-formation. The aerogel structure is
therefore directly related to the size and distribution of the ice
crystals in the frozen system. In addition, the thickness of the
aerogels plays an important role for the cooling rate. Thicker
samples cool more slowly. Samples with a thickness of 10 mm
were used in this study, whereas samples with thicknesses
between 1 and 5 mm were prepared by P€ a€ o et al.20
ak€
The fact that the aerogels have a structured porosity and
F morphology can be an advantage in various applications, for
example, as in the present work, for modifying the surface
51.0 wetting properties of the aerogel. The native cellulose nanofibers
are composed of cellulose I crystal domains as well as less
This journal is ª The Royal Society of Chemistry 2010

ordered fractions,33 and this promotes high length, flexibility,
entanglements, and robust networks of the so prepared aerogels,
even from very low NFC dispersion concentrations.20 As a result,
the present nanofibers make it possible to produce sponge-like
aerogels with a lower density than previous cellulose aerogels.57
This means that lower gel concentrations are needed for the
formation of robust aerogels that oppose collapse.20 In order to
decrease the density and to tune the porosity by creating large
pores, a surfactant has previously been used.21 In this study, no
additional surfactant has been used, but, as previously discussed,
a low density is due to fibrillar entanglement, and the porosity is
tuned by adjusting the concentration of the NFC dispersions.
Influence of the aerogel surface chemistry and surface texture on
Published on 14 May 2010 on http://pubs.rsc.org | doi:10.1039/C001939A
the wettability by oils
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The apparent contact angle q* for a composite interface beneath
a strongly non-wetting droplet is typically computed using the
Cassie–Baxter relation:59
cos q* ¼ f1cos q  f2 (1)
where f1 is the surface area of the liquid in contact with the solid
divided by the projected area and f2 is the surface area of the
liquid in contact with air trapped in the pores of the rough
surface divided by the projected area, i.e.:
area in contact with liquid
f1 ¼
projected area
and
area in contact with air
f2 ¼ (2)
projected area
The Lotus leaf is an example of a natural surface that is
forming a composite interface where water (glv ¼ 72.1 mN m1)
droplets form beads on the surface. This natural surface
comprises randomly distributed almost hemispherically topped
papillae with sizes 5–10 mm.60 The formation of the Cassie–
Baxter state enhances water super-repellency by promoting
a high apparent contact angle (q*) when f1  1.59
On the other hand, if the liquid fully penetrates into the surface
texture, the apparent contact angle q* is determined by the
Wenzel relation:61
cos q* ¼ rcos q (3)
where r is the surface roughness, defined as the ratio between the
actual surface area and the projected area. Since r is necessarily
greater than unity, roughness amplifies both the wetting and
non-wetting behavior of materials in the Wenzel regime, i.e., cos
q* [ 0 if cos q > 0 and cos q*  0 if cos q < 0 . A conse-
quence of this dependence on the roughness of the texture is that,
once initiated, the imbibition of a liquid drop into a roughened
texture can rapidly lead to super-wetting, because the apparent
contact angle q* / 0 when r [ 1 and q < 90 . Eqn (1) has
recently been rewritten as follows:62
f1 ¼ rff (4)
f2 ¼ 1  f (5)
This journal is ª The Royal Society of Chemistry 2010
View Online
cos q* ¼ rffcos q + f  1 (6)
where f is the fraction of the projected area of the solid surface in
contact with the liquid and rf is the roughness of the portion of
the solid in contact with liquid. When f ¼ 1, rf ¼ r in the Wenzel
model. It is important to note that rf in eqn (6) is not the
roughness ratio of the total surface, but only of that in contact
with the liquid. In this form of the Cassie–Baxter equation, the
contributions of surface roughness and of entrapped air are
clearer than in the other forms of the equation.62 The conditions
for highly non-wettability (q* [ 90 ) can be realized only in the
case of a composite interface where the solid–liquid contact area
is low. However, for low surface tension liquids with q < 90 , the
fully wetted or Wenzel state represents the thermodynamic
equilibrium state, whereas the composite interface or the Cassie–
Baxter state is metastable,45,50,63–65 representing a local minimum
in the overall Gibbs free energy. Thus, for low surface tension
liquids, the transition from a composite interface to a fully wetted
interface is irreversible, and typically this transition leads to
a loss of non-wettability. Therefore the ability to preserve this
metastable composite interface is crucial for engineering non-
wettable surfaces.66
In our previous work, we demonstrated how the incorporation
of a re-entrant surface texture (i.e., a multiscale surface topog-
raphy) in conjunction with surface chemistry can be used to
fabricate highly oleophobic surfaces, i.e., surfaces that can
support a robust composite (solid–liquid–air) interface and
display contact angles greater than 150 with various low-
surface-tension liquids such as castor oil and hexadecane.67 In the
present work, the development of NFC aerogels with different
surface textures has made it possible to fine-tune the surface
wettability, including the capacity to switch the surface wetting
properties between super-repellent and super-wetting against i.e.
castor oil.
The use of 1H,1H,2H,2H-perfluorodecyltrichlorosilane
(PFOTS) to generate oleophobic cellulose surfaces has been
discussed earlier.67 The high concentration of perfluorinated
carbon atoms in the alkyl chains leads to a very low solid-surface
energy for these molecules in the form of a thin layer structure
(gsv z 13.5 mN m1).67 As a comparison, the surface energy of
Teflon is gsv ¼ 18 mN m1.68 To provide a conformal and flexible
coating of PFOTS molecules on the NFC aerogels and films
possessing re-entrant and flat surface textures, respectively,
a simple chemical vapor deposition (CVD) procedure was used.
After the CVD, the equilibrium contact angle for castor oil on
a smooth NFC film increased to q z 96 compared to q z 0 on
an uncoated film. As previously discussed, a PFOTS-modified
aerogel is able to support a composite interface even with hex-
adecane (glv ¼ 27.5 mN m1), as shown in Fig. 6b. FE-SEM
micrographs showing the surface textures of aerogels with
various densities are shown in Fig. 3. A comparison with the
surface morphology of the PFOTS-coated aerogels (not shown)
shows that all the surface details, even features in the sub-
micrometre range, are preserved after modification.
As previously discussed, for a given surface texture, the non-
wetting properties can be most readily enhanced by markedly
lowering the surface energy of the solid, leading to increased
values of the equilibrium contact angle q (based on the Young’s
equation69). According to XPS measurements, the fluorine
Soft Matter, 2010, 6, 3298–3305 | 3303

concentration of the PFOTS-coated aerogels was 51  1%. The
variation in contact angle for castor oil on the aerogels is
therefore attributed to the variation in surface texture and should
be taken as the primary cause of the large difference in oleo-
phobicity. The tunable oleophobic properties of the PFOTS-
coated aerogels result from the rough and porous surface
textures and can be interpreted in terms of the Wenzel and
Cassie–Baxter models. It is clear in Fig. 5 that, for very low-
density aerogels (<0.0003 g cm3), the liquid is in contact with the
entire solid surface and completely penetrates the surface texture
generated by the multiple scale of roughness and pores, i.e.
Wenzel mode of wetting. The number of pores and the pore size
are most probably too large to enable these surfaces to support
a composite interface (Fig. 3a). More robust surfaces are
Published on 14 May 2010 on http://pubs.rsc.org | doi:10.1039/C001939A
obtained on higher density aerogels with a maximum in oleo-
phobicity (q z 166 ) at a density of 0.0070 g cm3 (Fig. 3d).
Downloaded by Nanyang Technological University on 31 May 2012
These properties are probably related to a fine balance between
the number of pores, the pore size and the extending sheet-like
structures protruding from the surface. Multiple scales of
roughness generated by protruding threads of fibril aggregates
probably also enhance the oleophobic properties. It is assumed
that there is no penetration of oil into the gaps and that the liquid
rests on the rough features of the protruding solid material. The
air bridging these features then acts as further support for the oil
droplet. The oil droplet can thus be considered to rest on only
a part of the solid surface exposing a large fraction of its surface
towards air and this situation can hence be modeled by the
Cassie–Baxter equation. However, as the number of pores
decreases for higher-density aerogels (>0.02 g cm3), a much
more closed and non-porous surface structure is obtained
(Fig. 3e and f). This simply results in a decreased surface area
which greatly resembles that of a smooth NFC film. A conse-
quence of this dependence on roughness is a transition from the
highly non-wetting state to the Wenzel state with q* z 96 .
The development of highly oil-repellent surfaces requires the
design of substrates that promote the formation of a composite
interface with almost any liquid. The two important character-
istics for arriving at a Cassie–Baxter state of wetting on
a textured surface with a given liquid are: (i) the magnitude of the
apparent contact angle q* on the composite interface and (ii) the
robustness of the composite interface against external pertur-
bation.66 Tuteja et al.45 developed a dimensionless design
parameter A* to predict the robustness of a composite interface.
This robustness factor represents the ratio of the breakthrough
pressure, Pbreakthrough, required to cause sufficient sagging and
disruption of the liquid–vapor interface, to a characteristic
pffiffiffiffiffiffiffiffiffiffiffiffiffiffi pressure Pref, given as Pref ¼ 2glv/lcap where lcap ¼
reference
glv =rg (here r is the fluid density and g is the acceleration due
to gravity). If the sagging becomes severe enough for the inter-
face to touch the underlying level of the solid texture, then the
composite interface collapses, and the liquid droplet rapidly
switches to a fully wetted state. The threshold pressure difference
that triggers the transition, i.e. the breakthrough pressure,
Pbreakthrough, can be computed as Pbreakthrough z A*  Pref. Thus,
large values of the robustness factor (A* [ 1) are associated
with the formation of a robust composite interface with a very
high breakthrough pressure.70
As previously discussed, the aerogels exhibit a random 3D
structural feature consisting of fibrils sheets and protruding fibril
3304 | Soft Matter, 2010, 6, 3298–3305
View Online
bundles, and it is difficult to systematically relate or model the
surface texture of the aerogels to the corresponding wetting
properties. Nevertheless, attempts have been made to systemi-
cally relate certain surface geometries to a robustness factor and
resulting wetting properties. Choi et al.66 designed geometrical
parameters for a texture dominated by periodical cylindrical
features; duck feathers, while Tuteja and co-workers45 analyzed
structural parameters governing the properties of super-oleo-
phobic electrospun fibers. They showed that for a given liquid
(given lcap), the robustness factor (A*) can be varied systemati-
cally, either by tuning the geometrical parameters describing the
surface (such as fiber radius and inter-fiber gap) or by changing
the equilibrium contact angle (q) through modification of the
surface chemical composition. It should, however, be stressed
that the authors used surfaces with well-defined periodically
arranged structures and fiber dimensions and that a similar
treatment of the interfaces in the present work demands a new
surface characterization procedure that is left for future studies
on these materials.
Conclusions
Native nanofibrillar cellulose aerogels have been prepared by
vacuum freeze-drying of aqueous dispersions of carboxymethy-
lated cellulose I nanofibers. The morphology and porosity of the
aerogels, as indicated by FE-SEM microscopy, can be tuned
simply by adjusting the concentration of the NFC dispersions.
A simple chemical vapor deposition process was developed to
achieve a conformal coating of low-surface-energy PFOTS
molecules on the aerogel surfaces. An XPS study of the chemical
composition of the PFOTS-modified aerogels confirmed the
reproducibility of the PFOTS-coating and the high atomic fluo-
rine concentration (ca. 51%) in the surface. The synergistic effect
of roughness, re-entrant topography of the aerogels, and the low
surface energy of the PFOTS molecules enables the CVD-coated
surfaces to support a composite interface with low-surface-
tension liquids such as castor oil and hexadecane. Advancing
contact angle measurements on the PFOTS-coated aerogels were
made, using castor oil as probe liquid. The results demonstrated
the very high oleophobic nature (q* [ 90 ) of the aerogels
compared to the corresponding contact angle (q z 90 ) for
a smooth NFC film. Aerogels with suitable surface textures were
developed allowing the systematical adjustment of their surface-
wettability characteristics. By combining this understanding with
a CVD process that provides a conformal fluorinated coating, we
can switch the wettability behavior of the cellulose surfaces
between super-wetting and super-repellent, using different scales
of roughness and porosity created by the freeze-drying technique
and change of concentration of the NFC dispersion.
Acknowledgements
The authors thank BIM Kemi Sweden AB and the Knowledge
Foundation through its graduate school YPK for financial
€
support. Profs. Lars Odberg and Lars Berglund are greatly
acknowledged for valuable discussions. M. Sc. Mikael Ankerfors
is gratefully acknowledged for supplying the NFC dispersions.
Dr Andrei Shchukarev at Ume a University is acknowledged for
performing the XPS experiments.
This journal is ª The Royal Society of Chemistry 2010

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