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Nanostructured biocomposites of high toughness - A wood cellulose

nanofiber network in ductile hydroxyethylcellulose matrix

Article  in  Soft Matter · August 2011

DOI: 10.1039/C1SM05325F

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Nanostructured biocomposites of high toughness—a wood cellulose nanofiber
network in ductile hydroxyethylcellulose matrix†
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Houssine Sehaqui,a Qi Zhouab and Lars A. Berglund*ac

Received 23rd February 2011, Accepted 1st June 2011
DOI: 10.1039/c1sm05325f

Nanopaper from wood-based nanofibrillated cellulose (NFC) offers vastly improved strength and
strain-to-failure compared with plant fiber-based paper and plant fiber biocomposites. In the present
study, unique nanostructural toughening effects are reported in cellulose nanofiber/
hydroxyethylcellulose (HEC) biocomposites. HEC is an amorphous cellulose derivative of high molar
mass and toughness. A previously developed preparation route inspired by paper-making is used. It is
‘‘green’’, scalable, and allows high reinforcement content. In the present concept, nanostructural
control of polymer matrix distribution is exercised as the polymer associates with the reinforcement.
This results in nanocomposites of a soft HEC matrix surrounding nanofibrillated cellulose forming
a laminated structure at the submicron scale, as observed by FE-SEM. We study the effect of NFC
volume fraction on tensile properties, thermomechanical stability, creep properties and moisture
sorption of the nanocomposites. The results show strong property improvements with NFC content
due to the load-carrying ability of the NFC network. At an NFC volume fraction of 45%, the toughness
was more than doubled compared with cellulose nanopaper. The present nanocomposite is located in
previously unoccupied space in a strength versus strain-to-failure property chart, outside the regions
occupied by microscale composites and engineering polymers. The results emphasize the potential for
extended composites mechanical property range offered by nanostructured biocomposites based on
high volume fraction nanofiber networks.

Introduction
For a long time, monolithic steel and aluminium alloys domi-
nated as load-bearing engineering materials in industrial appli-
cations. About fifty years ago, the development of strong,
microscale carbon fibers increased the interest in fiber composite
materials for aircraft structures, sports equipment and automo-
tive components. Today, the automotive industry is using large
amounts of glass fiber reinforced polymers. Glass fiber rein-
forcement improves strength and stiffness of polymer matrices,
but tends to reduce strain-to-failure. One reason is that weak
fiber–matrix interaction leads to the formation of interfacial
a
Department of Fiber and Polymer Technology, Royal Institute of
Technology, SE-100 44, Stockholm, Sweden. E-mail: blund@kth.se; Fax:
+46 8 207865; Tel: +46 8 7908118
b
School of Biotechnology, Royal Institute of Technology, SE-106 91,
Stockholm, Sweden. E-mail: qi@kth.se; Fax: +46 8 55378468; Tel: +46
8 55378383
c
Wallenberg Wood Science Center, Royal Institute of Technology, SE-100
44, Stockholm, Sweden
† Electronic supplementary information (ESI) available: (S1) Table of
parameters, (S2) creep and creep recovery fitting for neat HEC film
and NFC/HEC (34/51) biocomposites, and (S3) FE-SEM micrographs
of the surfaces of NFC nanopaper and NFC/HEC biocomposite
samples. See DOI: 10.1039/c1sm05325f
debond cracks at very low strain.1 The scale of the cracks is tens
of micrometres, and they tend to grow rapidly under loading.
Recently, the ambition to increase the proportion of materials
from renewable resources is manifested in increased use of plant
fiber–polymer matrix biocomposites.2,3 However, heteroge-
neously distributed microscale fiber reinforcement and weak
fiber–matrix interaction result in brittleness and low strain-to-
failure. Manufacturing is usually by traditional melt-processing.
In the context of new approaches, it is of interest to consider
concepts central to current soft matter research, such as envi-
ronmentally friendly hydrocolloidal processing systems and
material systems structured at the nanoscale for improved
hygromechanical performance.
As a source of inspiration, biological composites such as wood
tend to show remarkable toughness characteristics.4,5 The
reasons are complex, and related to the structure of biological
composites and associated deformation mechanisms.6 Compared
with man-made biocomposites, it is still clear that the nano-
structural characteristics of the plant cell wall are critical to the
toughness of plant structure biocomposites. For example, the cell
wall of wood typically has a thickness of a few micrometres
(earlywood), and yet consists of several hundred nanocomposite
layers.7 In the native plant, cellulose microfibrils of about 4
nanometres in lateral dimension are the reinforcing elements,

7342 | Soft Matter, 2011, 7, 7342–7350 This journal is ª The Royal Society of Chemistry 2011

and are embedded in a hydrated lignin–hemicellulose matrix.
The study by Keckes et al.5 on wet wood is particularly inter-
esting. The large ductility reported for the wood cell wall is
remarkable, as is the ability of the cell wall to preserve stiffness to
high strain.
Industrial biocomposites inspired by the plant cell wall are no
longer just a grand vision. High-quality cellulose nanofibers can
now be obtained by wood pulp fiber disintegration at low
cost.8–10 In order to emphasize the fine fibril dimension, the term
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nanofibrillated cellulose (NFC) is used in the present study rather
than microfibrillated cellulose (MFC). These nanofibers have
high length/diameter ratios, diameters in the 5–40 nm range, and
intrinsically favorable physical properties (i.e. a cellulose crystal
modulus of 134 GPa)11 due to the highly ordered extended chain
conformation of cellulose. Addition of small amounts of NFC
(<10 wt%) can improve the tensile strength by 20% in melt-
processed biocomposites.12 However, even higher NFC content
would be advantageous since Young’s modulus and tensile
strength can then be further improved. Compared with melt-
mixing, composites preparation from hydrocolloid NFC systems
makes it possible to realize much higher NFC volume fraction in
the biocomposite. Water is an environmentally friendly medium,
and can be readily recovered. Also, a well-dispersed NFC
hydrocolloid is likely to produce well-dispersed NFC bio-
composites, which is a challenge in melt-processing, although
melt-processing has the advantage of being the current tech-
nology for industries such as the automotive. Porous NFC
nanopaper sheets have previously been prepared by vacuum
filtration.13,14 A method to produce large, flat nanopaper sheets
was recently developed using a semiautomatic sheet former.15
Vacuum filtration was also developed as a technique for ‘‘nacre-
paper’’ sheets based on layered silicates16–18 coated with a poly-
mer matrix. In the present study, a water-soluble polymer matrix
and nanofibers are combined, without significant polymer loss
during filtration. In contrast with typical carbon nanotube
composites,19 the reinforcement content is very high and exceeds
50 percent by volume.
Previously, we studied composites based on cellulose nano-
fibers synthesized by Acetobacter aceti bacteria.20 The impor-
tance of this study was the creation of compartmentalized
bacterial cellulose (BC) nanofibers as HEC adsorbed to the
nanofibers during biosynthesis. HEC is a linear polymer of high
molar mass obtained by chemical modification of native cellulose
molecules. Compared with bacterial cellulose nanopaper, or
a physical blend of BC and HEC, the tensile strength of random-
in-the-plane oriented BC/HEC was much improved and
approached 300 MPa, due to the nanostructured morphology of
the biocomposite (individual nanofibers coated with a thin layer
of HEC). Despite the conceptual importance of the study on BC-
biocomposites based on polymer-coated nanofibers, large-scale
industrial applications require other manufacturing routes.
Furthermore, the strain-to-failure of the in situ synthesized BC/
HEC nanocomposite was limited to 6%.
Nanopaper13,21 and polymer matrix nanocomposites22 (starch)
based on high NFC content cellulose nanofiber networks show
high strength, high work to fracture, low thermal expansion,23
high thermal stability, exceptional barrier properties,24 and high
optical transparency.23 Favorable mechanical performance has
also been reported for bioinspired foams25,26 and low-density
This journal is ª The Royal Society of Chemistry 2011
View Article Online
aerogels27 based on NFC. In the context of the present study, the
high strain-to-failure (
10%) and the associated high work to
fracture (area under stress–strain curve) for cellulose nano-
paper13,21 are particularly interesting. The difficulty to realize the
mechanical property potential in nanocomposites has been dis-
cussed,28 and the lack of toughness has been pointed out as an
important reason.29 The unique characteristics of ‘‘soft’’ cellulose
nanofiber network composites are therefore interesting also in
a wider polymer nanocomposite perspective.
Nanostructured NFC–HEC network biocomposites of
different compositions are prepared by a water-based paper-
making approach in which HEC associates with the NFC. The
study focuses on mechanical properties. The NFC nanopaper
network by itself has high strength, and high toughness due to
a nanofiber slippage mechanism. This mechanism is further
exploited by addition of the ductile HEC matrix, which is
expected to coat the cellulose nanofiber surface. Indeed,
compared with any other composite material, the present bio-
composite has remarkably high toughness (work to fracture). In
addition, interesting effects from the NFC network on thermal
stability and creep behavior are reported.
Experimental
Preparation of NFC/HEC nanocomposites
NFC water suspension was prepared from never-dried softwood
sulfite pulp fibers (DP of 1200, lignin and hemicellulose contents
of 0.7% and 13.8%, respectively, Nordic Pulp and Paper, Swe-
den) according to a previously reported method.8 The pulp was
first subjected to a pretreatment step involving enzymatic
degradation and mechanical beating. Subsequently, the pre-
treated pulp was disintegrated by a homogenization process with
a Microfluidizer M-110EH (Microfluidics Ind., USA), and a 2 wt
% NFC suspension in water was obtained. HEC (2-hydroxy-
ethylcellulose, average Mv z 1 300 000 g mol1, substitution
degree 1.5, molar substitution 2.5 ethylene oxide groups per
anhydroglucose unit) was purchased from Aldrich.
HEC was dissolved in water with magnetic stirring overnight
to give a final concentration of 0.25 wt%. The 2 wt% NFC
suspension was diluted to 0.25 wt% by mixing with water in an
Ultra Turrax mixer (IKA, D125 Basic) for 10 min at 12 000 rpm.
Four different proportions of the 0.25 wt% HEC aqueous solu-
tion and 0.25 wt% NFC water suspension with the same total dry
weight (NFC + HEC) content of 450 mg were mixed using
a magnetic stirrer for 24 h, in order to ensure good mixing. The
mixtures were degassed and then vacuum filtrated on a glass filter
funnel using a 0.65 mm filter membrane (DVPP, Millipore),
according to the previously reported method for nanopaper.13
The wet cake, formed at the end of the filtration, was stacked
between metallic wire net and filter papers and then dried using
a laboratory sheet drier (Rapid K€ othen) at 93  C under vacuum
of ca. 70 mbar for 12 minutes. The thickness of the resulting
NFC/HEC nanocomposites was in the range of 65–80 mm. After
weighing the dry nanocomposite films, it was found that about
20% of the initial amount of HEC was lost (possibly a low molar
mass fraction). The neat NFC film (NFC nanopaper) was
prepared by the same filtration method without the addition of
HEC. The neat HEC film was prepared by solvent casting of
Soft Matter, 2011, 7, 7342–7350 | 7343

a degassed HEC solution at 0.25 wt% in a polystyrene Petri dish
under air atmosphere at room temperature. All samples were
conditioned at 50% relative humidity and 23  C for 1 week prior
to mechanical testing.
Density measurements, porosity and NFC volume fraction
calculations
The density of the materials (rce), including porosity, is deter-
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mined from samples ca. 2 cm wide and 4 cm long by measuring
the weight of the sample in air (wa) and immersed in mercury
(wHg). Knowing the density of mercury (rHg ¼ 13.534 g cm3),
and that of air (rair ¼ 0.0013 g cm3), the density of the sample is
given by:
wa
the ESI (S2)†.
rce ¼ r Hg  r air (1)
w a  w Hg
Porosity defined as the volume fraction of voids (VV) is calcu-
lated according to the following equations:
 
r ce
VV ¼ 1  (2)
r ct
1 humidity and 23  C, and their weights were recorded at different
r ct ¼
 (3)
Wf =r f þ 1  Wf r m
where rct is the density of the solid constituting the composite
(i.e. the density of non-porous composite). rf and rm are the
densities of NFC and HEC, and Wf is the weight fraction of
NFC.
The density of cellulose (rf) is assumed to be 1460 kg m3,30
while the density of HEC is assumed to be 1340 kg m3.31
The volume fractions of NFC (Vf) and HEC (Vm) are calcu-
lated from the weight fraction of NFC and from the density of
the films according to the following equations:
rct
Vf ¼ ð1  VV Þ Wf (4)
rf
Vm ¼ 1  VV  Vf (5)
Dynamic mechanical analysis (DMA)
Dynamic mechanical analysis (DMA) was carried out on a Q800
DMA analyzer (TA Instruments, USA) in tension mode. Speci-
mens used were of 5 mm in width, and the distance between
clamps was ca. 10 mm. Temperature scans were performed at
a heating rate of 5  C min1 and a frequency of 1 Hz from 50  C
to 300  C in air.
Creep test and modelling
Creep tests were performed using a Q800 DMA analyzer. Two
samples selected for this study are the neat HEC sample and the
NFC/HEC nanocomposite with volume fractions 34/51 percent
(the porosity of the biocomposite sample, i.e. 15 percent, was
determined on a sample of similar composition). The test was
conducted by subjecting the samples to a constant load of 10
MPa in air at various temperatures, 28  C and 80  C for the
7344 | Soft Matter, 2011, 7, 7342–7350
View Article Online
reference HEC sample and 28  C, 80  C, 120  C and 200  C for
the nanocomposite. The samples have similar geometry as those
used for DMA. The creep was recorded during 600 minutes at 10
MPa while creep recovery was recorded during unloading for an
additional 600 minutes.
From the loading/unloading creep curve, the elastic strain 30
was taken as the strain immediately after applying the load. The
modulus E0 was calculated by dividing the load (10 MPa) by 30.
3600 is the strain after 600 minutes of creep loading. The elastic
recovery represents the percentage of 3600 which is recovered just
after unloading the sample, while the total recovery is the
percentage of 3600 recovered after 600 minutes without load.
Creep loading and unloading curves were fitted with a nonlinear
viscoelastic model (Schapery model), and results are provided in
Moisture adsorption at 50% relative humidity
Samples were dried in a desiccator containing silica drying agent
at 23  C for 2 days. The dry weight was measured immediately
after the sample was removed from the desiccator. The samples
were then placed in a conditioned atmosphere at 50% relative
time intervals. The steady-state moisture adsorption at 50% RH
was recorded as no more increase in the weight of the sample was
observed.
Field-emission scanning electron microscopy (FE-SEM)
The dry specimens were fixed on a metal stub using carbon tape
and coated with a double-layer coating (ca. 5 nm) consisting of
graphite and gold–palladium using Agar HR sputter coaters. A
Hitachi S-4800 scanning electron microscope operated at 1 kV
was used to capture secondary electron images of the surfaces.
Tensile mechanical properties
Static tensile mechanical properties of the NFC/HEC bio-
composites were characterized using an Instron 5566 equipped
with a 500 N load cell. The tensile test was performed at
a controlled relative humidity of 50% and temperature of 23  C.
Rectangular specimen strips of 60 mm in length, 5 mm in width,
and a thickness in the range of 65–80 mm were tested at a strain
rate of 10% min1 and a gauge length of 30 mm. 3 specimens were
tested for each sample. Young’s modulus was determined from
the slope of the initial low strain region of the stress–strain curve.
The yield stress was taken from the intersection of the tangent of
the initial elastic region and the following plastic region.
Toughness, defined as the work to fracture, was calculated as the
area under the stress–strain curve.
In order to estimate the modulus of the NFC nanofibers,
a simple modeling approach for short fiber composites was
applied. Experimental values of the composite modulus were
fitted by a model for in-plane random fiber distribution by taking
the Young’s modulus of NFC in the longitudinal direction (El,
NFC) as variable. A best fit of the model to the experimental data
allows the estimation of El,NFC. An empirical equation,32 often
termed the Tsai-Pagano model, is used to estimate the in-plane
modulus:
This journal is ª The Royal Society of Chemistry 2011

3 5
Ec ¼ EL þ ET
8 8
where Ec is Young’s modulus of the random-in-the-plane
composite (experimental value of the composite modulus), EL is
longitudinal composite modulus (fibers parallel in one direction)
determined using eqn (7), and ET is transverse composite
modulus (transverse to fiber orientation) calculated using the
Halpin-Tsai model32 (eqn (8) and (9)).
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EL ¼ VfEl,NFC + (1  Vf)Em
1 þ 2hVf
ET ¼ Em
1  hVf
ðEt;NFC =Em Þ  1
h¼
ðEt;NFC =Em Þ þ 2
El,NFC, Et,NFC and Em are NFC longitudinal modulus, NFC
transverse modulus and matrix modulus, respectively. A value of
15 GPa was used for Et,NFC.33 Em was assumed to be 0.95 GPa
based on experimental measurements.
The parameters in eqn (1)–(9) are summarized in Table 1 and
in the ESI (S1)†.
Results and discussion
Preparation of NFC/HEC biocomposites
In previous studies where NFC hydrocolloids have been
combined with water-based polymer solutions or polymer
lattices, the aqueous mixture is typically dried in a Petri-dish for
about one week.34–36 The long drying time is in order to avoid
strong moisture concentration gradients through-the-thickness
of the film, so that it becomes as planar as possible. Here, the
procedure is significantly improved, see Fig. 1. Compared with
other methods for preparation of nanostructured material
systems, such as spin-coating37 or layer-by-layer deposition,38
a filtration approach is also much simpler and has potential for
further development to large scale industrial processes.17,18 In
Fig. 1, we start with one beaker of NFC hydrocolloid dispersion
and one beaker of HEC solution. The NFC hydrocolloid was
highly transparent and also stable. Flat and smooth NFC
nanopaper is prepared by a rapid vacuum filtration and drying
procedure. For preparation of NFC/HEC biocomposite films,
the NFC hydrocolloid was mixed with the HEC solution and
stirred. Again, the aqueous NFC/HEC mixture was highly
transparent and stable. We previously showed that as HEC is
added to the culture medium during biosynthesis of bacterial
cellulose, HEC adsorbs to the smallest cellulose nanofibers.20 It is
likely that similar mechanisms operate in the present case. In the
next step, the aqueous NFC/HEC mixture was vacuum-filtered
Table 1 Composition of the NFC/HEC composites and reference materials. Values within parentheses are standard deviations
NFC/HEC Vf/Vm 0/96 8/64
NFC weight fraction Wf (%) 0 12
Density rce/kg m3 1284 (53) 979 (17)
Porosity Vv (%) 4.2 27.7
NFC Vf (%) 0 8.0
HEC Vm (%) 95.8 64.3
This journal is ª The Royal Society of Chemistry 2011
View Article Online
(6)
(7)
(8)
Fig. 1 Preparation scheme for NFC nanopaper (arrow to the left) and
NFC/HEC biocomposites. A beaker of NFC hydrocolloid is combined
with an HEC solution and mixed. The mixture is then filtrated and dried
(9)
to a biocomposite film (bottom right).
and dried to a biocomposite film. Little loss of HEC occurred
during filtering. The pore diameter of the filtering membrane is
only 0.65 mm. The strategy to adsorb a water-soluble polymer on
the reinforcement phase is very interesting in order to avoid the
loss of polymer through the filtering membrane, and it also
means improved control of the polymer matrix distribution
(coats the reinforcement surface). Walther et al. used this
approach to prepare nanostructured clay-polymer nano-
composites by a paper-making procedure.17,18
The selection of polymer matrix is important in order to limit
the loss of polymer matrix through the membrane. Low molar
mass HEC, low molar mass polyethylene glycol (PEG), starch
and polyvinylalcohol (PVOH) showed a significant loss during
nanocomposite filtration attempts. In addition to high molar
mass HEC, polyethylene oxide (PEO of molar mass z 600 000)
could also be combined with NFC and vacuum filtered without
substantial PEO loss. These observations indicate that the
polymer needs to have (a) water solubility, (b) high molar mass
and (c) affinity to cellulose (association or adsorption). Our
results also indicate that the low molar mass polymer escapes the
NFC/HEC/water network hydrogel more quickly than the high
molar mass polymer. The paper-making preparation approach
using hydrocolloidal systems significantly widens the range of
volume fractions available to nanocomposite researchers.
DMTA
Thermomechanical properties of the NFC/HEC biocomposites,
pure NFC nanopaper, and neat HEC are presented in Fig. 2 as
storage modulus (E0 ) and tan d plots versus temperature. The
storage modulus of HEC shows a temperature dependence
characteristic of an amorphous high-Tg thermoplastic, with
a glass transition temperature of around 160  C (peak in tan d).
31/56 45/41 54/28 88/0
38 56 68 100
1202 (105) 1203 (58) 1168 (22) 1284 (38)
13.1 14.2 17.7 12.0
31.3 44.5 54.4 88.0
55.6 41.3 27.9 0
Soft Matter, 2011, 7, 7342–7350 | 7345
 View Article Online

Creep properties

Non-linear creep properties of neat HEC and the NFC/HEC 34/

51 biocomposites at high stress (10 MPa) are presented in Fig. 3
and summarized in Table 2. The main observation from Fig. 3 is
the significant reduction in creep of HEC as NFC is added. At 28

C, neat HEC showed an instantaneous elastic strain of 30 ¼
0.49% corresponding to a modulus E0 ¼ 2.1 GPa. After 10 hours
of loading at 10 MPa, the strain was doubled. Recovered strains
are also reported in Table 2. The biocomposites showed much
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reduced elastic strain 30 ¼ 0.14% corresponding to a modulus of

E0 ¼ 7.2 GPa. After 600 minutes, the biocomposite reached
a strain of only 3600 ¼ 0.24%. The recovered strains are also
higher than for the neat HEC, see Table 2. At close to room
temperature, the NFC network strongly reduces creep and also
increases creep recovery.
At elevated temperature (80  C), neat HEC failed at 10 MPa
load. The 34/51 NFC/HEC biocomposites showed high thermal
stability in terms of E0 at 80, 120, 200  C (5.9, 2.9 and 1.0 GPa).
3600 was 0.37% and 1.05% at the more reasonable temperatures of
80  C and 120  C, respectively. Since the Tg of HEC is around
166  C, it is not surprising that at 200  C the creep rate is high
and recovered strains are small, see Table 2.
In a previous study by Johnson et al.,35 creep properties of
HPC and NFC/HPC with 5 wt% NFC were reported. At 100  C,
the creep modulus after 10 min at 0.6 MPa was about 270 MPa
Fig. 2 (a) Storage modulus (E0 ) and (b) tan d as a function of temper- for NFC/HPC compared to 33 MPa for neat HPC. The present
ature for NFC/HEC biocomposites, pure NFC nanopaper (88/0) and NFC/HEC biocomposite showed a 10 minute creep modulus of
neat HEC (0/96). NFC/HEC volume fractions are provided next to each 1.8 GPa at 120  C and 10 MPa. This value is much higher than
curve. for NFC/HPC, due to the much higher NFC content (NFC
volume fraction 0.34). The excellent creep properties of the
present biocomposite are due to the mechanically robust and
thermally stable NFC network. With discrete non-creeping fibers
At temperatures exceeding 230  C, signs of thermal degradation
(glass fibers, carbon fibers), the short fiber composite creep strain
appear as E0 drops. There seems to be a strong secondary tran-
is caused by matrix creep. Here, the NFC network also
sition around room temperature, whereas E0 changes around 100
 contributes to the creep strain. The NFC cellulose nanofiber
C may be related to moisture evaporation.
itself does not show appreciable creep parallel to the nanofiber
The NFC/HEC biocomposites show strongly enhanced E0 at
direction. For this reason, stronger interfibril bonding is likely to
temperatures exceeding Tg of the HEC matrix. For an NFC
improve the creep resistance, although toughness may be
content above 31 percent by volume, E0 was higher than 2 GPa at
compromised (see coming section).
200  C. E0 was enhanced by a factor of 40 (from 6.5 MPa to 250
MPa) at 200  C when 12 wt% NFC was added to HEC.
Improvements of thermomechanical properties of NFC bio-
composites have been reported in previous studies.39–41 For
example, NFC/HPC (hydroxypropyl cellulose) biocomposites
with 5 wt% NFC have E0 ¼ 220 MPa at 150  C.35 The present
NFC/HEC biocomposites had E0 ¼ 1.3 GPa at 150  C with 12 wt
% NFC reinforcement. E0 was increased to 6.2 GPa at 150  C
with 68 wt% NFC. The data are also higher than those of glycerol
plasticized NFC/starch biocomposites, which had E0 ¼ 20 MPa
and E0 ¼ 3 GPa at 150  C with 10 wt% and 70 wt% of NFC,
respectively.22 The thermal stability of the biocomposites
increases with the NFC content, and reflects the thermo-
mechanical stability of the NFC network. Interestingly, for an
NFC volume fraction of 8%, the tan d peak at 165.8  C corre-
sponding to the Tg of HEC was shifted to 178.6  C due to the
reduced molecular mobility of HEC as it associates with cellu-
lose. The intensity of this peak was also considerably reduced in Fig. 3 Creep properties of neat HEC film and NFC/HEC (34/51) bio-
the presence of NFC, and completely suppressed at high NFC composite at 28  C at a constant stress of 10 MPa. Circles are experi-
content. mental data and solid lines correspond to curve fitting.

7346 | Soft Matter, 2011, 7, 7342–7350 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

Table 2 Creep data for HEC biopolymer and NFC/HEC (34/51) bio-
composites at a tensile stress of 10 MPa

Elastic Total
Vf/Vm T/ C E0/GPa 30 (%) 3600 (%) recovery (%) recovery (%)

0/96 28 2.1 0.49 0.94 41 73

34/51 28 7.2 0.14 0.24 61 84
34/51 80 5.9 0.17 0.37 42 66
34/51 120 2.9 0.34 1.05 26 53
34/51 200 1.0 0.98 6.68 6 17 Fig. 4 FE-SEM micrographs of the surfaces of (a) NFC nanopaper
(NFC/HEC ¼ 88/0) and (b) NFC/HEC (31/56) biocomposite.
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Moisture adsorption surface. The NFC/HEC 31/56 sample (right) with similar nano-
fiber distribution (random-in-plane orientation) did not show
Moisture adsorption of NFC/HEC was measured at a relative
apparent porosity since pores were filled by the HEC matrix.
humidity of 50% and 23  C, representing typical ambient
HEC is likely to be adsorbed or associated as a thin layer on the
conditions. The moisture adsorption data at steady-state for
NFC nanofibers, and excess HEC fills network pores. The
NFC/HEC biocomposites (Vf ¼ 8–54%), NFC nanopaper (Vf ¼
molecular interaction between HEC and NFC appears to be
88%), and neat HEC (Vf ¼ 0) are summarized in Table 3.
favourable (confirmed by NFC/HEC hydrocolloid stability and
Interestingly, these materials are not very hygroscopic and the
DMTA-observed shift in HEC Tg) although its detailed nature is
water content does not lead to degradation of mechanical
unclear. Additional FE-SEM surface micrographs of NFC/HEC
properties (see Section on mechanical properties in tension).
biocomposites of different compositions are provided in the ESI
Neat HEC was found to be only slightly more hygroscopic than
(S3)†.
NFC nanopaper (7.6% vs. 6.1% moisture content). Moisture
FE-SEM micrographs of tensile fractured cross-sections of
adsorption values for the NFC/HEC biocomposites are between
NFC nanopaper and NFC/HEC biocomposites are presented in
those of HEC and NFC.
Fig. 5. The laminated nature of NFC nanopaper (NFC/HEC 88/
0) is apparent. NFC nanofibers and bundles of NFC are also
apparent in the micrograph. Some fractured nanofiber ends
Microstructure of NFC/HEC biocomposites
appear as white dots. The laminated structure is typical for
Fig. 4 shows FE-SEM images of the surface microstructures of nanopaper13 and is probably related to flocculation phenomena
the NFC/HEC (31/56) biocomposite and NFC nanopaper. In in the high concentration region close to the filtering
both images, a swirled network of NFC is apparent. In appre- membrane.42
ciation of the fine structure one may note that the scale bar is 500 The NFC/HEC (54/28) biocomposite also displays a laminated
nm, whereas a typical plant fiber diameter in a microscale bio- structure. A very interesting feature is that the NFC-rich lamellae
composite or conventional paper is around 20–30 mm. The large are separated by HEC-rich interlaminar layers, see arrow in
aspect ratio (length/diameter ratio) of NFC is also apparent. upper right image. The thickness of this layer is around 100 nm.
Typical diameters are in the 10–40 nm range for the present In the NFC/HEC (45/41) biocomposite in the lower left corner,
NFC, and lengths exceed one micrometre. Furthermore, the HEC-rich interlayers are also observed. At the tip of the right
numerous interfibril connections are apparent. In the case of arrow, the ‘‘laminate structure’’ is apparent as a step in the
NFC/HEC the nature of the connections is unclear since an fracture surface. Also the left arrow is located in a lamella which
adsorbed HEC-coating layer is present, as documented in
a related study.20
The NFC nanopaper sample exhibits apparent pores with
a diameter of ca. 20 nm. These pores are formed as the nanofibers
are assembled in random-in-plane swirled mat distribution
during filtration. Observation of cross-sections indicates that
porosity is present through-the-thickness and not only on the

Table 3 Moisture adsorption data at steady-state for NFC/HEC bio-

composites, NFC nanopaper, and neat HEC at 50% relative humidity
and 23  C

Moisture
Vf/Vm adsorbed (%)

0/96 7.6
8/64 7.4
31/56 7.0
45/41 6.9
Fig. 5 Fractured cross-section SEM images of NFC nanopaper (NFC/
54/28 6.7
88/0 6.1 HEC ¼ 88/0) (a) and NFC/HEC biocomposite samples at NFC/HEC
volume fractions of 54/28 (b), 45/41 (c) and 31/56 (d). Scale bar is 500 nm.

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 View Article Online

protrudes from the fracture surface. These protruding lamellae

and steps result from interlaminar cracks forming during failure.
In the NFC/HEC (31/56) biocomposite, no laminar features are
immediately apparent, instead the HEC polymer matrix domi-
nates the fracture surface. Some matrix porosity is apparent, and
is estimated to be 13%. Nanofiber ends fractured in tension
appear as white dots and are distributed in the HEC matrix. The
pull-out lengths of the nanofibers appear very short.
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Mechanical properties in uniaxial tensile loading

The tensile stress–strain curves of the NFC/HEC biocomposites,
NFC nanopaper (88/0), and neat HEC (0/96) are presented in
Fig. 6. Young’s modulus, tensile strength, yield stress, and work
to fracture are presented in Fig. 7 as a function of the volume
fraction of NFC (Table 4).
The present NFC nanopaper samples have a typical tensile
strength of 175 MPa and a strain to failure of 8.5%. The most
remarkable results are for the 45/41 and 31/56 NFC/HEC
nanocomposites with strain-to-failures in the 19–24% range. At
the same time, the materials show strain-hardening so that the
NFC/HEC 45/41 reaches a strength of 180 MPa. Glass fiber
composites based on glass fibers in thermoplastic matrices such
as polypropylene may show high modulus and strength.43
However, the strain-to-failure is typically only around 2%,43 and
the present data are thus truly unique, in particular since the
constituents derive from biological resources.
The modulus data for the NFC/HEC biocomposites were fit
using the Halpin-Tsai and Tsai-Pagano models32 together with
matrix modulus data and assumptions for NFC transverse
modulus and geometry (discrete cylindrical fibers). The back- Fig. 7 (a) Young’s modulus, (b) tensile strength and yield stress, and (c)
calculated estimate for the axial NFC nanofiber modulus was 33 work to fracture of the NFC/HEC biocomposites as a function of the
GPa. This is lower than expected, and the main reason is that the volume fraction of NFC.
present NFC/HEC composites have matrix porosity in the 13–
27% range, which is not taken into account in the model.
The stress–strain curves of the NFC/HEC biocomposites HEC-coated NFC nanofibers from the matrix or simply associ-
showed interesting behavior. A first yield point is present at ated with onset of matrix shear yielding. An additional second
strains below 3%. In analogy with fiber/matrix debonding in ‘‘knee’’ is apparent on the curves at high strain. The deformation
microcomposites,1,44,45 this may be associated with debonding of mechanism behind this phenomenon is unknown but may be
related to the HEC-rich layers between NFC-rich lamellae or to
matrix voids. Complex mechanisms including slippage of nano-
fibers and plastic matrix deformation are involved in the plastic
deformation region. The second plastic deformation region
seems responsible for the unprecedented high strain-to-failure of
the present nanocomposites.
Young’s modulus as well as yield stress and ultimate tensile
strength all scale linearly with the volume fraction of NFC, see
Fig. 7(a) and (b). In nanocomposites research, due to
manufacturing challenges, a large proportion of the work is
focused on low volume fraction reinforcement effects, but the
data in Fig. 7 (made possible by the ‘‘paper-making’’ preparation
route) justify increased focus on high volume fraction nano-
composites. The combination of comparably high modulus, low
yield stress and high ultimate strength is unusual, and is caused
by a high volume fraction of a ductile cellulose nanofiber
Fig. 6 Stress–strain curves of NFC/HEC nanocomposites in uniaxial network combined with a low yield stress matrix, and some
tensile loading. The volume fractions of NFC/HEC are presented next to porosity.
the curves. 0/96 thus represents neat HEC and 88/0 is NFC nanopaper The NFC/HEC 31/56 nanocomposite combines relatively high
with 100 wt% NFC, with an estimated porosity of 12%. initial modulus with strain-hardening, high ultimate tensile

7348 | Soft Matter, 2011, 7, 7342–7350 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

Table 4 Tensile mechanical properties of the NFC/HEC composites and reference materials. Values within parentheses are standard deviations

NFC/HEC Vf/Vm 0/96 8/64 31/56 45/41 54/28 88/0

Young’s modulus Ec/GPa 0.95 (0.16) 1.87 (0.22) 4.58 (0.45) 7.50 (0.24) 8.23 (0.55) 9.93 (0.17)
Tensile strength/MPa 41 (7) 66 (2) 147 (6) 181 (5) 202 (5) 175 (2)
Yield stress/MPa 18 25 52 74 84 100
Specifc stiffness/GPa g1 cm3 0.74 (0.12) 1.91 (0.22) 3.81 (0.37) 6.23 (0.20) 7.05 (0.47) 7.73 (0.13)
Specific strength/MPa g1 cm3 31.9 (5.5) 67.4 (2.0) 122.3 (5.0) 150.4 (4.2) 172.9 (4.3) 136.2 (1.6)
Strain-to-failure (%) 36.6 (4.4) 32.5 (1.5) 24.4 (2.6) 19.0 (1.0) 14.0 (1.0) 8.5 (0.5)
Work to fracture/MJ m3 9.1 (2.1) 15.1 (0.6) 27.1 (4.1) 26.1 (1.5) 20.0 (1.7) 10.3 (0.7)
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Table 5 Work to fracture of biological and synthetic materials46

Work to
Material fracture/MJ m3

Wood (dry yew) 0.5

Steel (spring) 1.0
Horn (keratine) 1.8
Tendon (collagen) 2.8
Bone 3.0
Rubber (natural) 10.0
Mussel byssus thread 13.0
Abductin 13.0
NFC/HEC (31/56) 27.1
Bacterial cellulose/HEC20 (80 wt%/20 wt%) 11.0
NFC nanopaper13 15.1
NFC/glycerol plasticized starch22 (70 wt%/30 wt%) 9.4

strength and large strain-to-failure, the toughness expressed as

work to fracture (area under stress–strain curve) becomes as high
as 27.1 MJ m3. This is a true composite effect and about 3 times
higher than that of the individual components HEC and NFC
(9.1 and 10.3 MJ m3, respectively) (Fig. 7c). The maximum at
intermediate volume fractions is an interesting effect from the
composite nanostructure of the material and the associated
failure mechanisms. At higher volume fractions, strength is
favoured and ductility decreases.
Compared to some well-known tough biological and man-
made materials as well as other nanocomposites, the NFC/HEC
biocomposite is of exceptional toughness (Table 5). The only soft
matter-based material known to us of higher toughness is clay
platelet reinforced chitosan films.37 In a practical sense, the
preparation procedure in ref. 37 has the disadvantage compared
with the present approach in that each individual layer is laid
down separately in a highly elaborate process.
Zimmermann et al. reported on mechanical properties of
related composites based on NFC and HPC (hydroxypropyl
cellulose),36 although even at 12 wt% NFC the present materials
are superior to NFC/HPC with 20 wt% NFC. The most likely
explanation for this is in the NFC itself or in the organization of
the NFC network in the composite. The NFC network should be
formed from well-dispersed NFC and have a uniform structure.
The interlaminar HEC layers may also contribute favourably to
the failure properties of the present NFC/HEC composites.
NFC/HEC biocomposites show a unique combination of
strength and ductility for soft matter, and also in comparison
with many other categories of materials. The materials property
charts presented by MF Ashby are helpful in order to illustrate
this.47 As shown in Fig. 8, the NFC/HEC biocomposites of
high NFC contents (black dots) have similar strength as many
fiber composites but with much higher strain-to-failure (an
Fig. 8 Materials property chart48 showing strength versus elongation
(10% strain-to-failure corresponds to elongation ¼ 0.1). Note the log–log
scale. NFC/HEC nanocomposites of high NFC contents are represented
as black dots.
‘‘elongation’’ of 0.1 is the same as a strain-to-failure of 10%). The
‘‘elongation’’ for the nanocomposite is even similar to many
strain-hardening thermoplastics. The present nanocomposite is
thus situated in a region of property space previously unoccupied
by any soft matter material. Neither microstructured fiber
composites nor neat engineering polymers show this combina-
tion of properties. Short glass fiber/thermoplastic composites
typically have a tensile strength below 100 MPa and a strain-to-
failure below 3%.43 The present NFC/HEC strength of 180 MPa
therefore compares favourably with glass fiber reinforced
petroleum-based plastics presently used in automotive applica-
tions, with the added benefit of increased work-to-fracture and
biological origin. HEC adsorbs water, and effects on mechanical
performance need further study. A previous study on NFC
nanofiber network composites22 demonstrated that mechanical
properties are well preserved even with high liquid content
(glycerol) in the material. The reason is that the NFC network
dominates mechanical performance.
Conclusions
A wood-based biocomposite of remarkable toughness has been
presented. The toughness is related to the nanostructured char-
acteristics of a cellulose nanofiber network coated by a ductile

This journal is ª The Royal Society of Chemistry 2011 Soft Matter, 2011, 7, 7342–7350 | 7349

HEC coating. HEC is a linear polymer of high molar mass
obtained by chemical modification of native cellulose molecules.
As this nanocomposite of high cellulose content is loaded in
tension, the nanofiber network preserves its load-carrying ability
to unprecedented strains. At a volume fraction of 45%, the
strength is 181 MPa and the strain-to-failure is 19%. The
deformation mechanisms have been discussed, and in contrast
with glass fiber, carbon fiber and even carbon nanotube
composites, growth of visible large-scale cracks (>100 mm) can be
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delayed to strains in the range 10–20%.
The preparation of the nanostructured layered biocomposites
is done by applying a previously developed paper-making
approach, and HEC associates with cellulose nanofibers so that
only small amounts of polymer is lost during filtration. This
approach has advantages in a manufacturing perspective
(simpler than LBL and spin coating), but also provides nano-
structural control of the polymer matrix distribution (nanofiber
coating).
The NFC/HEC biocomposite shows significant thermo-
mechanical stability due to the NFC network. In addition, the
NFC network provides favourable resistance to creep. The
present concept of a stiff cellulose nanofiber network in a soft
matrix (low yield stress) results in a unique combination of low
yield stress, high ultimate strength, high toughness, thermo-
mechanical stability, limited moisture adsorption and high creep
resistance. As a consequence, this nanostructured and layered
biocomposite is located in property space previously unoccupied
by polymers or polymer composites, as illustrated in a materials
property chart of tensile strength versus strain-to-failure
(‘‘elongation’’).
Acknowledgements
Support from the Biomime center funded by the Swedish
Foundation for Strategic Research is gratefully acknowledged.
Ms Latifa Melk is gratefully acknowledged for skilled experi-
mentation and help with materials preparation. Dr Malin
Wohlert is acknowledged for help with modeling and data
reduction.
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