Research Article

www.acsami.org

Characterization of Pores in Dense Nanopapers and Nanobrillated

Cellulose Membranes: A Critical Assessment of Established Methods
Paola Orsolini,, Benjamin Michen,, Anja Huch, Philippe Tingaut, Walter R. Caseri,
and Tanja Zimmermann*,

Empa Swiss Federal Laboratories for Material Science and Technology, Applied Wood Materials Laboratory, CH-8600
Dubendorf, Switzerland

Institute for Building Materials and Multifunctional Materials, ETH Zurich, 8093 Zurich, Switzerland
S Supporting Information
*

ABSTRACT: Nanobrillated cellulose (NFC) is a natural

brous material that can be readily processed into membranes.
NFC membranes for uid separation work in aqueous
medium, thus in their swollen state. The present study is
devoted to a critical investigation of porosity, pore volume,
specic surface area, and pore size distribution of dry and wet
NFC nanopapers, also known as membranes, with various
established techniques, such as electron microscopy, helium
pycnometry, mercury intrusion, gas adsorption (N2 and Kr),
and thermoporometry. Although these techniques can be
successfully applied to inorganic materials (e.g., mesoporous
silica), it is necessary to appraise them for organic and
hydrophilic products such as NFC membranes. This is due to dierent phenomena occurring at the materials interfaces with the
probing uids. Mercury intrusion and gas adsorption are often used for the characterization of porosity-related properties;
nevertheless, both techniques characterize materials in the dry state. In parallel, thermoporometry was employed to monitor the
structure changes upon swelling, and a water permeance test was run to show the accessibility of the membranes to uids. For the
rst time, the methods were systematically screened, and we highlighted the need of uniform sample treatments prior to the
measurements (i.e., sample cutting and outgassing protocols) in order to harmonize results from the literature. The need for
revising the applicability range of mercury intrusion and the inappropriateness of nitrogen adsorption were pointed out. We
nally present a table for selecting the most appropriate method to determine a desired property and propose guidelines for
results interpretation from which future users could prot.
KEYWORDS: porosity, specic surface area, pore size distribution, mercury intrusion, gas adsorption, thermoporometry,
nanobrillated cellulose, membranes

1. INTRODUCTION

the development of water barrier papers, showing the need for

intercalating the nanobrillated cellulose with layered silicates
to achieve better performances in accordance to a berbrick
composite model, combined with a new native network model
and cover ber composite model:12 when adding layered
silicates into a NFC matrix, the water vapor permeance (WVP)
is lowered to 2.2 g/(m day Pa) from 6.4 g/(m day Pa) for neat
NFC lms. The same concept was shown by Wu et al.11 with
regards to oxygen-barrier properties.
Recent studies1420 propose the use of NFC for the
preparation of neat and composite membranes, targeting
mainly ultra- and nanoltration operations. NFC membranes
can easily be prepared by water removal from NFC
suspensions; for instance with a vacuum ltration process, the

Nanobrillated cellulose (NFC) is a biobased material that was

pioneered by Turbak et al.1 and subsequently studied over the
last three decades. NFC is extracted from plant cellulose pulps
or cellulose wastes, making it an abundant, renewable, and
sustainable material. It is isolated by wet processing methods,
such as high-pressure homogenization or grinding, which lead
to a gel-like substance composed of an entangled network of
cellulose nanobers. Such a material is frequently referred to as
nanopaper. The properties and applications of NFC nanopapers have been reported extensively in a series of reviews.28
One of the main applications can be found in the use of NFC as
barrier material for packaging because the material displays low
oxygen- and water-vapor-transmission rates913 due to the high
packing ability of nanobrillated bers and the existence of
crystalline domains.5,9,10 However, it was proven that by
increasing the relative humidity of the nanopaper its barrier
ability drops down.10,11 Our group also formerly contributed to
2015 American Chemical Society

Received: September 4, 2015

Accepted: October 30, 2015
Published: October 30, 2015
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brils self-assemble upon drying to give a meso- and
macroporous structure suitable for separation purposes. The
convenience of the process can be found in its simplicity and
reproducibility, leading to highly mechanically stable membrane
structures in the dry state21,22 with Youngs moduli between 6
and 17.5 GPa and tensile strengths between 100 and 250
MPa.21
NFC membranes possess a more sustainable life cycle and
performance comparable to those of membranes made of
petroleum-derived materials. A review by Carpenter et al.23
highlights the potential of NFC-derived fabricated membranes
in the eld of water treatment. NFC gained more relevance
over other nanocelluloses types because of better permeances
and better mechanical properties.24 Several cellulose-based and
-derived materials such as regenerated cellulose (RC), cellulose
acetate (CA), cellulose triacetate (CTA), and cellulose nitrate
(CN) were among the rst materials employed in the
development history of membrane processes.25,26 With regards
to these cellulose derivatives, NFC-based membranes possess
several advantages such as sustainability, the unnecessity of a
support layer in the membrane fabrication process and
narrower ltration ranges.
Similar to cellulose, NFC is insoluble in water but undergoes
swelling.27,28 A challenging issue that we address in our work is
the characterization of porosity-related properties of NFC
nanopapers or membranes in the swollen state compared to
those in the dry state. For this purpose, several methods based
on dierent working principles were employed on NFC
substrates so far. Permporometry allows for the determination
of active pores by forcing dierent probing uids through the
membranes (e.g., on the basis of liquid displacement, water10,12
and gas permeability,9,11,29 and bubble point measurements).
Spectroscopic methods (i.e., proton annihilation30) and
scattering methods (i.e., X-ray microtomography8) are also
available. In parallel, methods typically employed in membrane
science were applied for the characterization of NFC
membranes in the swollen state, such as water or solvents
ux, permeance, and the molecular weight cut o (MWCO),
corresponding to the molecular weight of known compounds
whose amount is rejected by 90% through a membrane.19,24 In
the present work, we critically assess dierent established
techniques regularly employed for characterizing other porous
NFC-based templates (i.e., foams or aerogels) also suitable for
fast industrial-quality assessment: electron microscopy, helium
pycnometry, mercury intrusion, gas adsorption, and thermoporometry were considered, respectively. Although they are
successfully used for other hydrophilic materials such as silica,
we analyze under which circumstances they partially fail for
NFC membranes because of their more pronounced hydrophilicity, compact structure, and surface chemistry and because
of dierent accessibility and wettability of probing uids (e.g.,
Hg, N2, Kr, and H2O).
In the present work, we provide information on the density,
specic surface area, total pore volume, pore size distribution,
and porosity of the NFC-based membranes and compare dry
and swollen states. To validate the correct use of the
aforementioned techniques, we assess them against inorganic
porous silicas used as reference materials with known pore
sizes.

volume used for calculations. The American Society for Testing

and Materials (ASTM) classies them as follows:31 theoretical
density is derived from the true volume (volume of the solid
excluding closed, blind, and open pores) of the material,
envelope density is derived from the envelope volume (volume
obtained by drawing the contour of a discrete piece of
material), skeletal density is derived from the skeletal volume
(volume of the solid and the closed and blind pores it may
contain), and bulk density is derived from the bulk volume
(volume occupied by the solid particles, including all pores and
also the interparticle voids). The bulk density changes with the
compaction of the material, where the interparticle void space
may rearrange by handling the product.
2.2. Mercury Intrusion. The mercury intrusion technique
applies to the characterization of pores in the so-called meso
and macro range (i.e., between 3 nm and 100 m). It is based
on the use of liquid mercury to probe the pores of solids and
largely incompressible substrates. Because the liquid mercury is
nonwetting, pressure is needed to force its penetration into the
pores. The theoretical development is therefore based on solid/
liquid interactions, the physical properties of mercury, such as
surface tension () and contact angle (), and mechanical
equilibria at the curved interface between the resistive force to
penetration of a pore aperture of radius (rp) and the
incremental pressure applied for the intrusion (P). The
relationship is summarized in the Washburns equation (eq
1),32 based on the assumption of a cylindrical pore shape,
derived from a modied YoungLaplaces equation.
P =

2 cos
rpore

(1)

The pressure needed for the Hg to penetrate the pores

apertures is inversely proportional to the pore radii. By
increasing the pressure up to 350 MPa, pores down to 3.0
nm can be investigated. In a typical mercury porosimetry
experiment, volumes of mercury intruded at each incremental
pressure are recorded, whereas the pore radii accessed are
calculated through eq 1. The technique provides information
about not only the voids present in the substrate (pores) but
also interparticle voids present between discrete pieces of the
substrate.33 For determining the porosity, the skeletal density
measured by helium pycnometry should be known prior to the
measurements. Information on the bulk density can be derived
after the measurements and further used for determining the
porosity of the sample. A hysteresis behavior is normally
observed between intrusion (along pressure increase) and
extrusion processes (along pressure decrease) because of the
pore shape, the tortuosity of the pores, and the substrate
surface chemistry. Because impurities might interfere with the
wetting behavior, samples must be dried or outgassed prior to
the measurements.
2.3. Gas Adsorption. Physical gas adsorption, known as
physisorption, is used to probe surface areas and pores. It relies
on the enrichment of a gas (adsorptive) on a solid substrate
(adsorbent). van der Waals interactions determine the
physisorption phenomenon controlling intermolecular forces
between the adsorptive and the adsorbent as well as binary
interactions among adsorptive molecules. The mathematical
formulation of the adsorption process in multimolecular layers
applied to porosity, known as BET model, was rst derived by
Brunauer, Emmett, and Teller in 1938.34 In a typical gas
adsorption experiment, an adsorption isotherm is generated by

2. THEORETICAL BACKGROUND
2.1. Density. Dierent types of densities can be determined
for porous materials such as membranes, depending on the
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ing micropores (<2 nm) because they are lled before

completion of the multilayer formation. A qualitative assessment of the micropore presence is given by the t-plot
method,35,37,38 where the adsorbed gas volume is plotted
against the theoretical thickness of the molecularly adsorbed
multilayer t and compared to the ideal case of a nonmicroporous substrate (pores >2 nm). Such samples have a
zero intercept. Accordingly, the presence of a positive intercept
for the tested sample provides an indication of the existence of
micropores.
A possible determination of pore volume and pore size
distribution from N2 desorption isotherms in the mesoporous
range was derived by Barrett, Joyner, and Halenda39 in 1951
and is known as the BJH method. Gas adsorption is carried out
until the relative pressure reaches 1; the understanding of the
adsorbate condensation process inside pores allows for the
characterization of the adsorbent pore size distribution. This
method assumes that ideal cylindrical pores are progressively
emptied upon relative pressure decrements, exploiting the
Kelvin radius rKn for the condensation of vapors inside
mesoporous cavities, the thickness reduction tn of the
adsorbate upon pore emptying, and the areas Ac of the pores
from where emptying occurs. The pore size distribution Vpn can
be derived by

measuring the amount of gas adsorbed onto the solid at

increasing adsorptive pressure and at constant temperature. By
decreasing the pressure, the desorption process can be
evaluated. To avoid interference with the adsorption process
and free all the available adsorption spots at the surface,
meticulous cleanings of the samples from any external impurity
have to be guaranteed. Normally, the samples undergo severe
outgassing protocols at high temperature and reduced pressure.
The adsorption isotherms have been classied by the
International Union of Pure and Applied Chemistry
(IUPAC) into six dierent types,35 corresponding to dierent
adsorptive/adsorbent interaction strengths and dierent surface
features.
Equations 2 and 3 (below) are used to calculate the surface
area (SSA):34
p
(C 1) p
1
= a +
n (p0 p)
nmC
nmaC p0

(2)

SSA(BET) = nmaLam /m

(3)

where na is the quantity of adsorptive adsorbed at the relative

pressure p/p0, nam is the quantity of the adsorptive needed to
cover the adsorbate with one monolayer, and C is a constant
varying according to the isotherm shape. The BET specic
surface area (SSA(BET)) is then calculated as in eq 3, where L
is the Avogadro constant, am is the molecular cross-section area
of the adsorptive and m is the mass of the adsorbent. Several
gases are available for the adsorption, such as nitrogen (N2),
argon (Ar), krypton (Kr), and carbon dioxide (CO2). In the
case of N2, am has a value of 16.2 2, and the isotherm is
generated at the boiling temperature of N2, 77 K. In the range
of relative pressures 0.05 < p/p0 < 0.30, the measured
adsorption points should result in a straight line in order to
satisfy the BET equation (eq 3). However, in some cases the
linearity does not extend up to 0.30 p/p0 for samples with
homogeneous surfaces of higher energy; in this case, Sing35
advises to report the correct range of linearity. The constant C
appearing in both in the intercept and in the slope of the
equation depends on the dierence between the heat of
adsorption of the rst monolayer E1, the heat of liquefaction EL,
the Boltzmann constant R, and the absolute temperature T. EL
is employed because the theory makes the hypothesis that the
evaporationcondensation behavior of any additional molecular layer after the rst one can be assumed equal to those of
the liquid state.34
C e(E1 E L)/(RT )

j=n

2
rpn
Vpn =
(Vn tn Acj )
rKn + tn/2
j=1

(5)

The BJH method is commonly used in literature for several

materials, and we use it to evaluate the PSD in NFC
membranes up to 100 nm.
2.4. Thermoporometry. Thermoporometry is a technique
that analyzes porous materials in the wet state. The sample is
soaked with a probing liquid (e.g. water) that undergoes a shift
in freezing and melting temperature (T) when conned in
pores with diameters in the submicrometer range. The physical
phenomena is explained by the GibbsThomson eect40,41 and
allows us to associate T with the pore radius (rp). Brun et al.42
correlated those temperature-phase transition shifts, evident in
dierential scanning calorimetry (DSC) measurements, to the
size and shape of pores. Measuring in an excess of the probing
liquid produces the formation of two enthalpy peaks in typical
melting or freezing DSC thermograms. One peak is attributed
to the excess free water on the surface of the sample (FW)
undergoing a phase transition at about 273.15 K, and other
peaks at lower temperature are related to water conned or
bound within pores (BW). The aforementioned T corresponds to the dierence between the peak position of free and
bound water and is related to the pore radius. The derivation
made by Brun limits the applicability of the thermoporometry
to the mesoporous range. Micropores (<2 nm) cannot be
probed because the liquid is prevented from freezing in such
pores as a result of the added contribution of surface energy.
Generally, the nonfreezable water (NFW) covers a thickness
of two to three molecular layers in pores of inorganic materials,
thus amounting to a thickness of ca. 0.8 nm. For organic
materials, however, the values of have to be determined. In
addition, macropores are also excluded from the characterization because the calorimetric peaks related to the transition
shifts of the water in the pores cannot be well-separated from
the free water melting at 273.15 K. After determining several
binary surface tensions of liquids on solids (sl), Brun and coworkers42 derived a semiempirical correlation (eq 6) for

(4)

The parameters appearing in eq 4 suggest that caution has to

be paid for systems in which particularly weak or strong
interactions occur between adsorbent and adsorptive because
the packing behavior of the adsorptive might be altered while
generating the multilayer. According to Rouquerol,36 in the
case of low values of C, reliable values of nam are obtained if the
knee of the isotherm is relatively sharp (i.e., the BET constant
C is below 100). A very low value of C (<20) refers to a
mixture of monolayer and multilayer adsorption; therefore, the
BET analysis does not provide reliable values. Krypton
adsorption has to be employed for samples with small specic
surface areas (i.e., <2 m2/g)35,36 because its precise detection is
more reliable than that of N2 for low volumes of adsorbed gas.
The BET theory fails not only for systems with weak
adsorbent/adsorptive interactions but also for systems contain25886

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3.3. Methods. 3.3.1. Scanning and Transmission Electron

Microscopy. Scanning electron microscopy (SEM) was executed
using a FEI Nova NanoSEM 230 Instrument (Fei, USA), at an
accelerating voltage of 5 kV. A transmission electron microscope
(TEM) Jeol JEM-2200FS (Jeol USA Inc., USA) with eld emission
was utilized at 200 kV to observe Davisil, silica gel 60, MSU-H, and
SBA-15. Sample preparation and image evaluation were carried out
using the software ImageJ and are reported in Supporting Information
sections 1.4 and 2.3 and Figures S2S3.
3.3.2. Thermal Gravimetric Analysis. Thermal gravimetric analysis
(TGA) experiments were conducted using a TGA 7 (PerkinElmer,
USA). Details about the methods are available in Supporting
Information section 2.2 and Figure S1.
3.3.3. Skeletal Density by Helium Displacement Pycnometry and
Envelope Density. Helium pycnometry measurements were conducted using an AccuPyc II, 1340 (Micromeritics Inc., USA). The
skeletal density of the materials was evaluated at 20 C. NFC
membranes were cut in to irregular pieces (1 mm 1 mm),
subsequently dried at 90 C for 1 h, and kept in a desiccator. The
skeletal volume was nally determined by displacements with an inert
gas.
Membrane density was also determined as the ratio between their
mass m and their volume, as described in Supporting Information
section 2.1, and we referred to this as envelope density.
3.3.4. Mercury Intrusion. Pascal 140 and Pascal 440 mercury
porosimeters (Thermo Fisher, Germany) were utilized to record the
measurements for low- (up to 120 kPa) and high-pressure intrusion
(up to 350 MPa) at room temperature. Eventually, data were
combined with the software S.O.L.I.D. Silicas and NFC membranes
were dried at 90 C for 1 h and kept in a desiccator. Sample masses
between 1.40 and 1.70 g were employed. The density of Hg was
automatically corrected at room temperature, whereas the advancing
contact angle and the surface tension were dened as 140 and 0.48
N/m, respectively. A maximum vacuum of 0.3 kPa was reached during
outgassing of the samples.
3.3.5. Gas Adsorption. An Autosorb iQ2 (Quantachrome, USA)
was employed for N2 and Kr gas adsorption experiments. Inorganic
materials (Davisil, silica gel 60, MSU-H, and SBA-15) were outgassed
for 16 h at 150 C with ultimate vacuum of 5 107 Pa,53 reached
with a turbomolecular drag pump. NFC membranes were blade-cut in
small pieces (1 mm 1 mm) to ll the measuring cells, without
compromising the nature of the membrane system as a whole. To see
the eect of moisture on NFC membranes, dierent cleaning
protocols in terms of temperature and time were carried out: (i) 30
C for 15 h, (ii) 90 C for 15 h, and (iii) 90 C for 45 h. Other
samples were conditioned at 20 C at dierent relative humidities
(RH; 35, 65, and 85%), until a constant mass was registered. For these
samples, the measuring cells were lled, weighed, sealed in the
conditioning room, and connected to the machine rapidly. The latter
were not subjected to any outgassing procedure. Kr adsorption was
carried out by outgassing the samples at 90 C for 45 h as well. NFC
foams were outgassed at 90 C for 45 h for determination of SSA, pore
volume, and pore size distribution.
3.3.6. Thermoporometry. Thermoporometry was carried out with a
DSC apparatus (Mettler DSC822e; Mettler-Toledo Intl. Inc. Instrument, USA). The samples were rst equilibrated at 40 C and
afterward heated up at a rate of 0.25 C/min under N2. Three to four
replicates were always run, and the enthalpy data were averaged with
respect to the temperature.
The machine was calibrated with indium, as reported in the
standard procedure from Mettler-Toledo. DSC scans were acquired
for the water employed in the measurements. Raw data are available in
Supporting Information section 4.3 and Figure S9.
NFC disks of 4 mm in diameter were punched out of the
membranes and allowed to swell in deionized water (conductivity of 7
S/cm at 22 C) for dierent swelling times: 5, 24, and 200 h. For
each swelling time, three membranes were prepared, and four replicas
were measured for each membrane. The disks were removed from the
swelling medium, the excess of water was dried on a clean tissue, and

probing inorganic materials under the assumption of cylindrical

pores:
rp = A

B
T

(6)

A (nm) and B (nm K) are numerical coecients that change

with the probe liquid employed and with the phase transition
occurring (melting/freezing). According to Brun, in the case of
water melting and under the assumption of cylindrical pores,
the A and B coecients assume the following values: 0.68 and
32.33 nmK, respectively, and the validity of eq 6 is limited to
values of T between 40 and 0 C. However, for T > 2
C, the relationship assumes an asymptotic behavior with
respect to the pore radius rp, making the derived PSD
questionable. Hay and Laity43 showed a dependency of the
peaks position with the scanning speed; as a consequence, the
maximum pore size detectable can change accordingly. On the
basis of the correlation of Brun between T and rp (d(T)/
drp)), Landry et al.44 provided an equation (eq 7) to transform
the heat ow signal of the DSC thermogram (dQ/dt) into pore
size distributions (dVp/drp). Other parameters were also taken
into account such as the sensitivity of the instruments through
the scanning rate employed (d(T)/dt), the solid mass of the
dry sample m, and the physical parameters of the liquid such as
its density (T) and its specic melting enthalpy (Hf(T)).
dVp
drp

dQ dt d(T )
1
dt d(T ) drp m H f (T ) (T )

(7)

Water has been widely utilized as probing liquid on

hydrophilic materials such mesoporous silicas45,46 and
cellulose4749 and for the evaluation of membrane pore
structures.50,51

3. EXPERIMENTAL SECTION
3.1. Materials. Never-dried cellulose bers were provided as
elemental-chlorine-free pulp (ECF) with a water content of 70 wt %
(Zellsto Stendal, Germany). The ECF pulp is composed of 3040%
pine and 7060% spruce bers. Silica gel 60 of 230400 mesh, SSA
450540 m2/g, pore size of 6 nm, and pore volume of 800 mm3/g was
purchased from Merck (Germany). Davisil, grade 646 with 3560
mesh, SSA 300 m2/g, pore size of 15 nm, and pore volume of 1150
mm3/g, and mesostructured silica MSU-H with pore size of 7.1 nm,
SSA 750 m2/g, and pore volume of 910 mm3/g were purchased
from Sigma-Aldrich (Germany). For the synthesis of SBA-15
(Supporting Information section 1.1), hydrochloric acid (37%) and
pluronic P-123 were purchased from Sigma-Aldrich (Germany).
Tetraethoxysilane was obtained from Evonik Industries (Germany).
Liquid mercury 99.9995% was purchased from Sigma-Aldrich
(Germany). Caution! Care has to be taken when handling mercury.
Work in agreement with the safety rules of your country and follow risk and
safety instructions reported on the mercury datasheets.
3.2. NFC Membranes and NFC Foams Preparation. NFC was
prepared by a grinding and homogenization method, as thoroughly
described in Supporting Information section 1.2. For preparing the
membranes, 0.75 g of dry matter NFC was diluted in deionized
(conductivity of 5.2 S/cm at 22 C) water to a nal volume of 400
mL. The suspension was stirred at 10 000 rpm for 1 min with a Digital
Ultra Turrax T25 (Ika, Germany) and later outgassed under vacuum
for 20 min to remove air bubbles. The suspension was poured onto a
standard ltration apparatus, ltered by vacuum to obtain a wet cake of
NFC, and nally hot-pressed for 20 min at 1000 N/mm2 and 120 C.
Membranes (150 g/m2, 110 0.07 m thick) were thus produced.
Additional details are available in Supporting Information section 1.3.
To produce NFC foams, the NFC suspension was diluted to 1 wt %
and processed by freeze-drying as reported elsewhere by Zhang et al.52
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the sample was sealed inside 40 L aluminum pans (Netschz,
Germany).
MSU-H, SBA-15, silica gel 60, and Davisil in powder form were
inserted into the aluminum pans and put in contact with a water drop.
The masses of the samples were recorded before and after the
measurements in order to ensure that the Al pans remained sealed
during the scanning. After the measurements, the crucibles were
punched twice with a needle (diameter, 1 mm) and dried in an oven at
105 C to evaluate the total mass of water taken up by the samples.
3.3.7. Water-Permeance Tests. Water-permeance tests were carried
out for NFC membranes after swelling in deionized water for 5 days at
room temperature. The membranes were placed in a high-pressure cell
HP4750 (Sterlitech, USA). The cell was loaded with 250 mL of
deionized water and subjected to incremental nitrogen pressure from 0
to 4 bar over time. Membranes with grammages of 30, 50, 100, 150,
and 200 g/m2 were tested. The permeated water was recorded over
time via a precise balance (Sartorius, Germany).

4. RESULTS AND DISCUSSION

First, the morphology of the materials was evaluated by
electron microscopy (section 4.1). Thereafter, densities of
silicas and NFC membranes were characterized by helium
pycnometry and mass-to-volume ratios (section 4.2), mercury
intrusion (section 4.3), gas adsorption (section 4.4), and
thermoporometry (section 4.5). A nal section pays specic
attention to the results reproducibility (section 5).
4.1. Morphology and Average Diameter of Mesoporous References and NFC Membranes. TEM microscopy was employed to characterize porous silicas (images and
evaluations available, Figure S2). The dp for Davisil and silica
gel 60 could not be clearly determined because of their
nondened structure. In contrast, for MSU-H and SBA-15
highly ordered hexagonal framework patterns were visualized
with dp of 5.7 1.0 and 5.2 0.9 nm (MSU-H and SBA-15,
respectively). Pore sizes are in agreement with manufacturers
data and the literature.54,55
SEM images of NFC (Figure 1a) showed a typical network
structure with nanobers of polydisperse diameters below 100
nm and lengths of several micrometers. (Precise determination
is not possible.)5
Although in Figure 1b the surface of an NFC membrane with
a few voids and randomly arranged brillar aggregates can be
visualized, Figure 1c presented highly porous cross sections that
were mainly composed of interconnected random-in-plane
NFC sheets interposed with spherical voids and longitudinal
cracks with no dened shape. Meso- and macropores were both
present. Although the brous nature of NFC generates pores
whose structure cannot be ascribed to any simple geometrical
shape, the assumption of cylindrical pores was made for the
other characterization techniques considered in this work. This
structural anisotropy originated from the self-assembly process
of NFC upon water removal.
The pores present in the cross section were evaluated using
ImageJ by taking the pore contour (Figure 1d) and deriving the
pore diameter from the area of an equivalent circle (additional
info in the Supporting Information section 2.3 and Figure S3).
The histogram in Figure 1e displayed an abundancy of pores in
the range between 40 and 300 nm. Pores smaller than 40 nm
were underestimated with the achieved magnication of
50 000, invalidating the counts of pores at the border of
this range. We thus assume that a large fraction of pores 40
nm could not be visualized. Pores larger than 400 nm were
suspected to be the longitudinal cracks mentioned before,
which might not belong to the original membrane architecture.

Figure 1. SEM micrographs of (a) NFC, (b) NFC membrane top

view, (c) NFC membrane cross section, (d) contour-lines evaluation
of pores, and (e) pore size distribution. Error bars represent the
Gaussian deviation.

SEM micrographs were acquired under high vacuum (105

106 mbar) and reduced moisture contents; thus, no swelling
was accounted for in the structure. Sizes were reduced because
of the sputtering layer (7 nm for cross-sectional micrographs, 2
nm for top views) that should be taken into account. SEM can
be used as a qualitative but not quantitative tool for pore
characterization.
4.2. Evaluation of NFC Membranes Densities. The
density of the reference materials and NFC membranes were
rst determined by helium pycnometry in order to calculate the
porosity of the materials after drying at 90 C for 60 min.
Values between 2.15 and 2.25 g/cm3 were measured for the
skeletal density, consistent with the literature.56 For NFC
membranes, a value of 1.506 0.002 g/cm3 was obtained,
which does not dier drastically from the theoretical density of
cellulose (1.541.56 g/cm3 for cotton bers)57 and is in
agreement with the values reported elsewhere for pressed NFC
lms.58,59 This indicates that a negligible portion of closed
pores was present. The envelope density of the membranes was
also determined by weight-to-volume ratios after drying at 90
C for 60 min, resulting in a value of 1.44 0.03 g/cm3
Compared to the skeletal density, the envelope density
underestimated the value by roughly 0.06 g/cm3 because of
an overestimation of the sample volume. In fact, when
measuring the thickness by means of a caliper, the maximum
thickness accounts for the maximum roughness values. The
porosity (P%) of the samples was calculated as follows:
P% =
25888

(skel env )
skel

100
(8)
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where skel and env are skeletal and envelope densities,
respectively. From a skeletal density of 1.44, in agreement
with the density value of solvent casted NFC lms from Minelli
et al.,10 a value of porosity 4.65% was obtained, as
summarized in Table 1. Quing et al.60 determined the envelope

cally dried nanopapers. The higher compaction we achieved

might be related to the presence of a considerable amount of
small nanobrils.61
4.3. Pore Volume, Pore Size Distribution, Average
Pore Diameter, and Porosity by Mercury Intrusion. Prior
to the measurement, a mild outgassing of the sample is
generally carried out that rarely brings to vacuum below 0.3
kPa. Under these conditions, it was not possible to estimate the
amount of removed adsorbates. In a typical experiment, the Hg
volume uptake is reported against the intrusion and extrusion
pressure. For silica materials, S-shaped curves (Figure 2a) were
obtained. As expected, a steep increase of Hg uptake occurred
under high pressure (40 MPa), corresponding to the lling of
pores smaller than 35 nm, whereas typical hysteresis loops
appear because of the irreversibility of the intrusionextrusion
process. Some dierences in the curve shapes of disordered
mesoporous silica (viz. Davisil and silica gel 60) and cylindrical
silicas (viz. MSU-H and SBA-15) were visible because of the
phenomenons dependency on the pore structure as explained
by Coasne et al.62
For NFC membranes (Figure 2b), the volumetric data
showed an initial steep lling of the intermembrane voids,
followed by a plateau in the range of 0.0520 MPa. A second
increase in Hg uptake was observed above 20 MPa and was
attributed to lling of the pores. The hysteresis loop was
narrower for NFC membranes compared with that of the silica
materials but was almost constant along all radii domains,
suggesting that the extrusion process was less irreversible for
membranes than for reference materials. According to Wardlaw
et al.,63 this result might suggest that the pathways that the Hg
had to take to extrude the samples were shorter in the NFC
membranes than in the silicas because of smaller pore throats to
pore cavity ratios.
By employing Washburns equation (eq 1), the PSD can be
derived as shown in Figure 2c,d. MSU-H and SBA-15 presented
narrower distributions as compared to those of Davisil and
silica gel 60, with pore volumes of hundreds of cubic milimeters
per gram as reported in Table 1 and in agreement with the

Table 1. Results on Reference Materials and NFC

Membranes of Skeletal Density Determined by Helium
Pycnometry and Envelope Density, Followed by Bulk
Density, Accessible Porosity, Pore Volume (Vp), and
Average Pore Diameter (dp) Determined from Mercury
Intrusion Porosimetry

skeletal density
(g/cm3)

Davisil

silica gel
60

MSU-H

SBA-15

NFC mem

2.15

2.17

2.25

2.24

1.51 0.002

envelope density
(g/cm3)

1.44 0.03

P%a
bulk density
(g/cm3)
P%b
P%d
P%e
Vp (mm3/g)
dp (nm)

4.65
Determination by Hg Intrusion
0.58
0.47
0.21
0.18
86
63.0
73.1
791
13.3

81
38.9
78.3
293
5.7

94
57.7
90.6
607
5.2

c
64.0
92.0
795
6.0

1.36 0.01
13.3 0.5
5.5
9.8 1.1
38.4 1.8
28.6 2.3

Dierence of skeletal and envelope densities, after drying at 90 C, 60

min. bValue determined by S.O.L.I.D. software, including artifacts and
intermembrane voids. cValue not consistent. dPorosity calculated by
eq 9, pore volume taken between 1 and 100 nm. ePorosity calculated
by eq 10.
a

density and porosity of NFC lms prepared from dierent

cellulose sources and obtained results between 1.32 and 1.38 g/
cm3 and porosities between 8.5 and 12%. Lower density values,
and consequently higher porosity, are achieved for vacuumdried nanopapers, solvent-exchanged nanopaper, or supercriti-

Figure 2. (a) Hg intrusion volumetric data for silica reference materials and (b) for four replicates of NFC membranes, respectively; pore size
distribution determined by converting the volumetric data through Washburns equation for (c) reference materials and (d) NFC membranes.
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Figure 3. Nitrogen adsorption isotherms showing the volume adsorbed under standard conditions (Vol (STP)) versus that adsorbed under relative
pressure p/p0 for NFC membranes treated dierently prior the measurement: outgassing at (a) 30 C for 15 h, (b) 90 C for 15 h, and (c) 90 C for
45 h; conditioning at (d) 35% RH, (e) 65% RH, and (f) 85% RH.

through eq 8. The porosity could also be calculated by

comparing the bulk density to the skeletal density, as in eq 10.

manufacturers specications. Concerning NFC membranes

replicates, their PSD overlaid, conrming their high reproducibility, and pore volumes were in the order of a few cubic
milimeters per gram. The full PSDs are available in Figure S4.
The total pore volume (Vp) and the average pore diameter (dp)
were calculated from the PSD curves in a denite pore size
range to exclude the contribution of Hg uptake by interparticle
voids (Supporting Information sections 3 and 4.1). The values
obtained are reported in Table 1. The dp of silica materials
matched the expected values; for NFC membrane, dp was 28.6
nm with a peak at about 5 nm when integrating the PSD until
100 nm, including fully the mesoporous range. Because pores
below 3.7 nm were not measured and pores above 100 nm were
excluded, their contributions to the total pore volume and to
the PSD were not considered. The Vp obtained was 38.4 mm3/
g.
The accessible porosity was computed by the machine
S.O.L.I.D. software by comparing the bulk density obtained by
Hg intrusion to the skeletal density determined by helium
pycnometry (Table 1). A value of 13.3 0.5% was found when
considering the full pore size distribution up to the macropore
range. However, this value is higher than the porosity estimated
by the dierence between skeletal and envelope density
(4.65%) because of the overestimation of the total pore
volume including macrocracks and intermembrane voids,
making the values generated by the software not always
trustworthy. By considering the pore volume in the range of
3.7100 nm obtained by the integration (38.4 mm3/g) and the
skeletal density of the membranes, the porosity in this range
can be calculated as in eq 9, resulting in a value of 5.5%. This
latter was in closer agreement with the density determined

P% =

P% =

Vp
Vp +

1
skel

100

skel bulk
skel

(9)

100
(10)

In this case, a value of 9.8% was calculated. All results presented

were determined without any compressibility correction. The
limited compressibility of NFC membranes was assessed by a
double-intrusion experiment (Figure S6). Ferraz et al.14
obtained PSD of porous composite nanocellulose lms with a
dp of 21 nm, comparable with the NFC membranes.
4.4. Specic Surface Area, Pore Size Distribution,
Total Pore Volume, and Average Pore Diameter by Gas
Adsorption Technique. To validate the gas adsorption
technique, measurements were rst run on silica reference
materials. S-shaped type-IV isotherms were observed by N2
adsorption (raw data in Figure S7). Davisil and silica gel 60
presented an hysteresis loop of type H1, typical of materials
obtained by the consolidation of spheres.35 MSU-H and SBA15, exhibited hysteresis between type H1 and H4, indicating the
presence of a network of micro- and mesopores.64 In a second
step, the correct operation of the machine was conrmed with
highly porous cellulosic nanomaterials, such as NFC foams
obtained by freeze-drying (raw data and image of foams in
Figure S7). Results for the NFC foams returned a value of SSA
of 16.8 1.3 m2/g, R2 of 0.999965, C of 59.3, and Vp of 73 5
mm3/g. Because N2 adsorption results were in agreement with
the widely available data in the literature for such
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Table 2. Values of SSA, R2, C Constant, and Intercept of t-Plot Method for Reference Silica Materials Determined by Means of
N2 and Kr Adsorption with Outgassing at 150 C for 16 h
outgassing

Davisil

silica gel 60

MSU-H

SBA-15

150 C, 16 h

150 C, 16 h

150 C, 16 h

150 C, 16 h

gas ads

N2

Kr

N2

Kr

N2

Kr

N2

Kr

conditioning

none

none

none

none

none

none

none

none

SSA (m2/g)
R2
C
t-plot intercept

237.0
0.9997
68.48
15.7

293.2
0.9999
29.09

366.09
0.9999
118.67
24.9

351.3
0.9998
26.92

835.95
0.9999
164.57
111.5

994.9
0.992
190.73

704.9
0.9999
118.72
48.6

637.8
0.9998
34.32

Table 3. Values of SSA, R2, C Constant, and Intercept of t-Plot method for NFC Membranes Determined by Means of N2 and Kr
for Dierent Outgassing Protocols and RH Conditionings
NFC mem
outgassing

30 C, 15 h

90 C, 15 h

90 C, 45 h

90 C, 45 h

none

none

adsorptive

N2

N2

N2

Kr

N2

N2

N2

conditioning

none

none

none

none

35% RH

65% RH

85% RH

SSA (m2/g)
R2
C
t-plot intercept

0.137 0.014
0.9999
11.60
0.03

0.126 0.016
0.997
12.14
0.01

0.199 0.0268
0.9996
11.05
0.03

0.095 0.008
0.9999
8.82

0.138 0.028
0.9999
14.61
0.006

0.175 0.016
0.9994
8.33
0.038

0.184 0.008
0.9923
6.34
0.035

none

Figure 4. (a) PSDs of reference materials, (b) cross section of a blade-cut NFC membrane, (c) PSDs for NFC membrane samples purged with
dierent outgassing conditions, and (d) PSDs of NFC samples conditioned under dierent RHs.

products,6567 we concluded that the machine was operated

properly.
The measurements were then repeated on NFC membranes;
specically, the impact on their PSD of the outgassing
conditions and the presence of moisture in the membranes
were investigated. Adsorption isotherms were recorded with N2
(Figure 3) and Kr at 77 K (Figure S8).
For all outgassing conditions and relative humidities,
unlimited adsorption35,64 occurred at high relative pressure
(p/p0 = 1; Figure 3). Such a behavior appears for systems
presenting pore ranges extending above the range covered by
gas adsorption, typically of a few hundred nanometers. Because
of the nonlimited adsorption, the shape of the isotherms at low
p/p0 appeared at; however by magnifying the low relative

pressure region, one could classify them as type IV. The

membranes isotherms, as presented, referred to the volume of
N2 adsorbed per total mass of the sample. In our case, it
corresponded either to a sum of cellulose and moisture content
(because of unremoved pollutants or to the moistening
process) or only to cellulose when a valid outgassing was
carried out. A decrease of the maximum volume of N2 per gram
of sample was observed at p/po = 1 when increasing RH, which
highlighted that water molecules present at the surface of the
nanobers interfere with the adsorption of N2.
4.4.1. Determination of SSA by Nitrogen Compared with
Krypton Adsorption. The adsorption isotherms measured at 77
K with N2 and Kr allowed for the determination of SSA,
correlation coecient R2, C constant, and the value of the t-plot
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higher fraction of pores in the range of 413 nm could be

obtained by applying a longer purging time. Apparently the
purging treatment removed most of the adsorbed species,
mainly water moisture, which lled the pores or clogged up
their entrances. Seemingly, water moisture at 77 K might
undergo freezing, reducing the available space for the nitrogen
to adsorb. We suppose that the nitrogen adsorption did not
always proceed through multilayer formation but rather
through a disturbed adsorption in the presence of water
molecules which interfered with the nitrogen condensation
process in the pores. These outgassing conditions (90 C and
45 h) were found to be the most suitable purging parameters
through an investigation by an isothermal TGA analysis. The
latter was carried out and is discussed in Figure S1. A clear
trend in changes of total Vp cannot be seen. In parallel, N2
adsorption measurements were repeated for samples conditioned with increasing RH (35, 65, and 85% RH). Signicant
changes for the PSD were found for 35% RH compared to
those of 65 and 85% RH (Figure 4d). As shown in Figure 4d,
the total pore volume, corresponding to the areas below PSDs,
was signicantly reduced for the samples conditioned at 85%
RH (Vp = 0.27 mm3/g) compared to that of samples
conditioned at 35% RH (Vp = 0.55 mm3/g). This eect was
attributed to a swelling of the nanobers, which entailed a pore
size reduction and prevented the accessibility of the gas
molecules to the pores as compared with drier states. The
porosity in all cases was determined as a function of the pore
volume and the skeletal density (1.51 g/cm3), as in eq 10.
Detailed results obtained by integrating the curves up to 100
nm are summarized in Table 5.
As for the PSD, the total pore volume was also inuenced by
the outgassing and the conditioning protocols. Upon
calculation of the porosity through the pore volume obtained
by this technique, the limitations of nitrogen adsorption on the
characterization of NFC membranes were strongly highlighted.
A maximum value of 0.1% was found for outgassing protocol iii
(90 C, 45 h), whereas the determination of porosity formerly
carried out in this work returned a value of 4.65% by eq 8, 5.5%
by eq 9, and 9.8% by eq 10. The average pore diameter was not
very much aected by the dierent conditions, varying in the
range of 24.335.3 nm. Despite the averaged values, two peaks
of the PSD were observed at 3 nm and between 5.4 and 12.9
nm. In all samples, longitudinal cracks introduced during
sample preparation (Figure 4b) might correspond to voids
where N2 condensation did not occur, thus causing unlimited
adsorption. PSD between 4 and 100 nm resembled the one
obtained by Ferraz et al. with N2 adsorption algae nanocellulose
membranes,14 measured after outgassing at 95 C for at least 24
h. In our case, a more pronounced fraction of pores below 4 nm
was revealed, which might be due to a more polydisperse
distribution of nanobrils diameters.

intercept for reference silicas and for the NFC membranes are
reported in Tables 2 and 3, respectively.
The SSA of the reference materials matched the
manufacturers values. High values of C constant were found
(C > 50). A positive t-plot intercept was determined for MSUH (111.525) and SBA-15 (48.59), indicating that these samples
own micropores (pores <2 nm).
For NFC membranes, the p/p0 was assessed to be in the
range of 0.15 and 0.2 m2/g when measured by means of N2
adsorption. A visible impact of the moisture content on the SSA
could not be appreciated; moreover, one should note that the
absolute area held by the measuring cell was below 2 m2/g,
requiring an additional investigation by Kr. Kr adsorption,
known to give a more precise determination,35,36 resulted in
lower p/p0 of 0.095 0.083 m2/g. The BET method generated
high correlation coecient, R2; however, in all cases, the C
constant remained below 50 independent of the outgassing
protocol, suggesting the existence of weak interactions between
nitrogen and adsorbent.68 In our study, a decrease in C value
was observed with increasing the relative humidity, which
conrms that water molecules interfere with the adsorption of
N2 on the sorbent. Values of the t-plot intercept were close to
zero for all NFC membranes investigated, suggesting that no
micropores (pores <2 nm) were present.
4.4.2. Determination of the Pore Size Distribution and
Total Pore Volume by Nitrogen Adsorption. The PSD for the
reference materials and the NFC membranes were derived from
N2 adsorption isotherms by means of the BJH method and are
presented in Figure 4a.
The total pore volume and the average pore diameter are
summarized in Table 4. The properties provided by the product
manufacturers and the PSD obtained by Hg intrusion agreed
with the N2 adsorption results for all references.
Table 4. Total Pore Volume (Vp) and Average Pore
Diameter (dp) for Reference Materials by Nitrogen
Adsorption
Davisil

silica gel 60

MSU-H

SBA-15

outgassing

150 C, 16 h

150 C, 16 h

150 C, 16 h

150 C, 16 h

gas ads

N2

N2

N2

N2

conditioning

none

none

none

none

Vp (mm3/g)
dp (nm)

1190
11.3

796
6.3

780
7.4

805
8.1

In the case of NFC membranes, increasing the outgassing

temperature from 30 to 90 C for 15 h did not change the PSD
signicantly (Figure 4c), which is in agreement with their
hysteresis proles. However, a modication of the PSD was
noted when the samples were kept at 90 C for 45 h. Here, a

Table 5. Porosity (P%), Average Pore Volume (Vp), and Average Pore Diameter (dp) for NFC Membranes by Nitrogen
Adsorption with Dierent Outgassing and Conditioning at Dierent RH
NFC membranes
outgassing

30 C, 15 h

90 C, 15 h

90 C, 45 h

none

none

gas ads

N2

N2

N2

N2

N2

N2

conditioning

none

none

none

35% RH

65% RH

85% RH

P%
Vp (mm3/g)
dp (nm)

0.08
0.50
24.3

0.08
0.51
35.3

0.10
0.66
24.3

0.08
0.55
30.6

0.08
0.55
27.2

0.04
0.27
30.7

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Figure 5. DSC thermograms indicating free water peaks (FW) and bound water peaks (BW) of (a) reference material and (b) NFC membranes at
swelling times of 5, 24, and 200 h. PSD for (c) reference materials (y axis 104) and (d) NFC membranes.

Table 6. Pore Volume (Vp) and Pore Diameter (dp) Data Obtained by Thermoporometry
Davisil

silica gel 60

MSU-H

SBA-15

8.24 104
11.6

5.25 104
7.0

7.09 105
6.2

1.35 105
6.1

swelling time
Vp (mm3/g)
dp (nm)

NFC mem
5h

24 h

200 h

0.49
28.7

0.37
28.8

0.35
28.6

Equation 7 was employed to transform the heat ow data into

PSD (Figure 5c,d). The average pore size for reference
materials matched condently the ones investigated by gas
adsorption and Hg intrusion where the materials were
evaluated at dry state. In contrast, the total Vp was lower by
7 orders of magnitude. For cylindrical-shaped MSU-H and
SBA-15, we assume that the penetration of water from both
openings of the cylinders caused trapping of air bubbles,
resulting in an apparent pore volume being strongly underestimated. For Davisil and silica gel 60, a transition to the gel
state might have occurred being responsible for the void
volume reduction.
Concerning NFC membranes, the impact of the swelling
time on the PSD, Vp, and dp of the NFC membranes was
investigated for 5, 24, and 200 h. Independently from the
swelling time, the FW and the BW peaks were overlapped,
which prevented us from resolving the full peak corresponding
to the BW (Figure 5b). The FW peak measured on membranes
was at temperatures between 0.33 to 0.38 C, which was lower
than those for reference materials and pure water. Laity et al.43
reported that in cellulose membranes the cellulose itself can act
as heterogeneous catalyst for ice formation. This may lead to a
lower melting temperature of water and explain our
observations. Because the full heat ow signal could not be
exploited, the PSD for the NFC membranes was generated
using only data points below T of 2 C. The heat ow
above this value was neglected.
In Figure 5, the PSDs of NFC membranes are shown; a
dependency on the swelling time was clearly observed. The
distributions accounted for a value of nonfreezable water layer
(), as determined by Brun. As Maloney already reported,69

We conclude that the outgassing protocols and moisture

content have a strong impact on the measured properties; thus,
in order to compare the results in the literature, a good practice
would be to harmonize the preparation of samples and
outgassing protocols before executing the gas adsorption
measurements on NFC membranes.
4.5. Total Pore Volume, Pore Size Distribution, and
Average Pore Diameter by Thermoporometry. Thermoporometry was employed to characterize the materials in the
wet state. We veried the calibration of the machine by utilizing
the method on the reference materials, of which average size
and pore volume were known from the manufacturer data and
from former investigations in this work. Afterward, the
measurements were carried out on NFC membranes. In
addition, pure deionized water samples of dierent masses (1
24 mg) were run in order to determine a representative FW
peak for the analysis in this work. It is worth mentioning that
the peak position is mass-dependent because of the dierent
heat capacities of increasing masses of water drops. For 1 mg of
water, the FW peak lays at 0.49 C, whereas for 24 mg, it is at
1.35 C. The average FW peak position was taken at 0.91 C as
calculated from multiple measurements of pure deionized water
(Figure S9).
In Figure 5a,b, respectively, representative DSC thermograms
for the melting ramps of reference materials and the NFC
membranes are displayed. For the mesoporous silica references,
the enthalpy signals for BW were located in the range of 25
and 3 C and clearly appeared well-separated from the FW
peak located between 1 and 1.5 C. The FW peak position
changed compared to that of deionized water (0.91 C)
because of the anity between hydrophilic silica and water.
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Table 7. Comparison of Average Pore Diameter (dp) and Pore Volume (Vp) Results between Values Known from the
Manufacturers and Values Determined by the Considered Techniques for the Investigated Silica Materials and NFC
Membranes
manufacturer
Davisil
silica gel 60
MSU-H
SBA-15
NFC mem

SEM/TEM
3

dp (nm)

Vp (mm /g)

15
6
7.1

1150
800
910

dp (nm)

Hg intrusion
3

Vp (mm /g)

5.7
5.2

N2 adsorption
3

thermoporometry
3

dp (nm)

Vp (mm /g)

dp (nm)

Vp (mm /g)

dp (nm)

13.3
5.7
5.2
6.0
28.6

791
293
607
795
38.4

11.3
6.3
7.4
8.1
24.3

1190
796
780
805
0.66

11.6
7.0
6.2
6.1
28.7

Vp (mm3/g)
8.2
5.3
7.1
1.4
0.5

104
104
105
105

5. MEASUREMENT REPRODUCIBILITY
The results obtained for the reference silica materials with the
three porosimetry techniques were in good agreement with
each other and with the data provided by the manufacturers,
whereas signicant variations were noted for NFC membranes
depending on the technique employed. This was mainly due to
the use of dierent probing uids, pretreatments, and range of
applicability. With regards to the reproducibility, Hg intrusion
generated highly reproducible curves for NFC membranes,
conrming the repeatability of membrane preparation process.
In N2 and Kr adsorption, the importance of determining a
proper outgassing protocol was highlighted: With mild
outgassing (viz. protocols i and ii) the reproducibility of the
measurements was low; however, by purging the samples at 90
C for 45 h, it increased. DSC thermograms showed highly
reproducible curves for all dierent swelling times. However,
FW and BW peaks were not suciently resolved to perform a
complete evaluation of NFC membranes properties.
By considering each single property investigated in our work,
we observed the following: Hg intrusion was not used for the
derivation of SSA values because we cannot exclude the
contribution of surface generated by sample preparation. Gas
adsorption on NFC membranes was employed to estimate the
SSA. By N2 adsorption, the values were below 2 m2/g; thus, to
overcome this problem, Kr adsorption was employed. The SSA
diminished by half compared to that obtained via N2
adsorption. This conrmed an anomalous behavior of nitrogen
not in agreement with multimolecular adsorption BET model.
The low value of Kr SSA conrmed the membranes high
packing density in which brils strongly clustered upon drying.
With regard to the PSD, none of the techniques allowed for a
direct measurement of micropores (<2 nm). Hg intrusion
permitted the characterization of pore diameters above 3.7 nm;
nevertheless, the cracks not originally belonging to the
membrane cannot be distinguished in the macrometer range.
In the case of N2 adsorption, the relevance of the outgassing
protocols was brought up by showing how extensively the
shape of the PSD changed in the presence of unremoved
adsorbate.
Dierent techniques returned dierent values because of the
dierent penetration of the probing uids employed. Hg
intrusion occurs with limited penetration in the inner cavities of
tortuous pores, leading to underestimated porosity values.
However, it was the method that returned a closer porosity
value to the one determined by eq 8. The low pore volume
determined by N2 adsorption (0.66 mm3/g for protocol iii) was
highly underestimated because of an anomalous adsorption
process. Finally, thermoporometry did not allow the determination of porosity at all.

this value is still unknown for cellulosic materials. Results for

total pore volume and average pore diameter were derived by
analyzing the PSD in the pore size range between 3 and 30 nm
(as explained in Supporting Information section 3) and are
summarized in Table 6. A decrease in the relative pore volume
was observed with increasing swelling time, whereas the dp
remained constant.
Interestingly, the PSD shape obtained through thermoporometry diered from what could be visualized by gas
adsorption and mercury intrusion in the dry state. We
hypothesize that in the presence of liquid water a swelling of
the whole membrane structure took place giving rise to an
increase of volume between the bers; thus, bigger voids and
parallel closing of the pores may have occurred because of the
swelling of the adjacent bers. In this case, NFC membranes in
water appeared to have bigger pores as compared to those
obtained by dry state techniques, with a distribution starting
above 10 nm and a peak in the upper limit of the mesoporous
range. A second hypothesis could be that in the presence of
cellulose the nonfreezable water layer ( 1.6 nm for silicas) is
thicker than two to three molecular layers;43 thus, pores might
exist but are lled by liquid water. Consequently, no heat ow
signals for crystals melting in those ranges can be visualized
because crystals cannot form. Assuming a diameter of 0.275 nm
for the H2O molecule, pores of a 10 nm size should be lled by
36 layers of water. We believe that a combination of the two
phenomena occurred for NFC membranes.
4.6. Water-Permeance Tests. As a proof of concept that
NFC lms produced by vacuum ltration can display
membrane functions, water permeance tests were carried out
(raw data in Supporting Information section 4.4). The
permeance signicantly decreased upon grammage and thickness increases, corresponding to higher ow resistance. For
membranes with grammages of 30 and 50 g/m2, water
permeation started when a pressure of 2 bar was applied, and
permeances of 18 and 9 L/(h m2 MPa) were recorded,
respectively. However, from grammage of 100 g/m2 on, at least
4 bar was needed to operate the ltration. The values for
grammages of 30 and 50 g/m2 are in full agreement with the
results obtained in the work of Mautner et al.,24 where the
rejection ability of the membranes was also investigated by
molecular weight cut o (MWCO) of PEG. It was shown that
NFC membranes had a MWCO of 25 kDa targeting nano- and
ultraltration operations. The need of boosting the overall
permeance, through the porosity of the membranes, and
keeping the pore size distribution narrow arose from these
outcomes; modications in the processing method should be
introduced when preparing the membranes to be competitive
with industrially available membranes for nano- and ultraltration. This is the object of our present investigations.
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Table 8. Summary of Properties That Can (viz., Yes) or Cannot Be (viz., No) Reliably Determined by Each Technique under
Certain Conditions Claried in the Footnotes
(g/cm3)
He pycnometry
m/V ratio
electron microscopy
Hg intrusion
N2 adsorption
Kr adsorption
thermoporometry

P%

SSA (m2/g)

dp (nm)

PSD (mm3/g/nm)

total Vp (mm3/g)

Vp(1100 nm) (mm3/g)

no
yesd
no

no
no
no
yes
no

no
yes
yes

40 nm m
3.7 100 nm
2 100 nm

no
no
noe

no
yes
no

no

3 30 nm

no

no

yes
yesb
yesc

no

In the dry state, skeletal density. bIn the dry state, envelope density. cIn the dry state, bulk density. dUnder the condition of excluding pores below
3.7 nm and void artifacts. ePore clogging does not allow N2 permeation

theless, challenges were faced when evaluating the results

because of the fact that the PSD extends over the macroporous
range, which is neglected by this technique. The determination
of the pore size and, thus, the ltration range can be assessed
indirectly by determining the molecular weight cut o
(MWCO)19,24 of polymer solutions in water. In this study,
only the water permeance through membranes of dierent
grammages was appraised; however from this preliminary data,
the need of increasing the porosity arose. This is subject of a
work we are dealing with at present.
We nally created a table to be used as a guideline tool for
other researchers to pinpoint the use of the appropriate
characterization method for a wanted property. The density of
dry NFC membranes should be determined by helium
pycnometry; its pore volume and average pore diameter in
the mesoporous range (i.e., 3100 nm) should be determined
by mercury intrusion. For determining the SSA, we advise the
use of Kr adsorption prior a reliable outgassing protocol (such
as at 90 C for 45 h under vacuum for membranes of grammage
150 m2/g). The inappropriateness of nitrogen adsorption
was articulated. The characterization in the swollen state
remained unsolved; still, the rearrangement of the 3D structure
of the membrane was revealed, moving one step further with
the existing characterization and partially invalidating the
information deducible at the dry state: Closing of pores in
the lowest mesoporous range shifted the distributions to higher
pore diameters.
We believe that the main ndings of our investigations could
be applied and extended to other bio- and cellulosic
nanomaterials, such as bacterial cellulose and cellulose
nanocrystals membranes.

From all former evaluations, a comparative table (Table 7)

collecting the main results for total pore volume and pore
diameter was compiled.
One can visualize a good agreement of results for reference
materials, whereas scattering of results for pore volume of NFC
membranes is brought to the foreground. Although the pore
volumes determined by N2 adsorption and thermoporometry
were comparable, both appeared underestimated compared to
that of mercury intrusion. In the case of N2 adsorption, we
supposed a clogging mechanism of pore entrances and their
partial lling by moisture. In thermoporometry, closing of pores
occurred at low pore sizes because of the swelling. In Table 8,
we summarize the properties, such as porosity, SSA, PSD, dp,
and Vp, that can be determined by each technique in a reliable
way, not fully reliably, or that cannot be determined at all. Such
a table might serve as a guideline for future researchers dealing
with the characterization of dense, nonchemically modied
NFC membranes and provide awareness on the validity of
obtained results.

6. CONCLUSIONS
We carried out the characterization of dense NFC membranes
by means of dierent dry- and wet-based techniques. Although
several methods were considered, it was not possible to identify
a universal one for the determination of all examined
properties, such as total pore volume, porosity, average pore
diameter, and pore size distribution.
Overall, the impact of the sample preparation was
emphasized. Macrocracks that do not originally belong to the
porosity of the sample are introduced when blade-cutting the
membranes. To overcome the problem, one should consider
fracturing the membranes in liquid nitrogen to prevent the
alteration of newly generated interfaces.
In the presence of moisture, pores in the lowest fractions of
the mesoporous range remained hidden when performing N2
adsorption. A combination of an isothermal TGA coupled with
a mass spectroscopic measurement in vacuum would be
benecial to monitor degradation processes.
Three of the techniques employed (i.e., He pycnometry, Hg
intrusion, and N2 adsorption) evaluated the properties of NFC
membranes in the dry state; however, once installed in ltration
units, the membranes are supposed to work in aqueous
environment. As to future recommendations, an investigation
by a volumetric water vapor adsorption combined with dynamic
gravimetric water vapor sorption (DVS) at dierent relative
humidities should be investigated. This would allow for a better
understanding of water diusion and membrane swelling.
An attempt to characterize the NFC membranes in water
medium was made by employing thermoporometry; never-

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acsami.5b08308.
Synthesis of SBA-15, NFC production and NFC
membranes detailed preparation, electron microscopy
imaging details, script for data integration, mercury
intrusion full-PSD and double-intrusion experiment, N2
adsorption on reference materials and NFC foams, Kr
adsorption on MFC membranes, DSC scan for water and
thermoporometry raw data, and water permeance raw
data. (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: Tanja.Zimmermann@empa.ch.
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Funding

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EMPA is kindly acknowledged for nancial support.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We thank Dr. K. Feldman for support with DSC measurements
and F. Rechberger and Dr. E. Tervoort-Gorokhova from ETH
Zurich for support with gas adsorption. We kindly acknowledge
Esther Strub for SEM imaging and all group members for
valuable discussions.

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