Composites Science and Technology 69 (2009) 500–506

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Composites Science and Technology

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c o m p s c i t e c hX

Reduced water vapour sorption in cellulose nanocomposites with starch matrix

Anna J. Svagan, Mikael S. Hedenqvist, Lars Berglund *

Department of Fibre and Polymer Technology, Royal Institute of Technology, S-100 44 Stockholm, Sweden

nanofiber network (70 wt% cellulose nanofibers) reduced

the moisture uptake to half the value of the pure plasti-cized
starch film. The swelling yielded a moisture concentration-
dependent diffusivity. Quite surpris-ingly, the moisture
article info diffusivity decreased rapidly with increasing nanofiber
abstract content and the diffusivity of the neat cellulose network
was, in relative terms, very low. It was possible to describe
the strong decrease in zero-concentration diffusivity with
Article history: increasing cellulose nanofiber/matrix ratio, simply by
assuming only geometrical blocking using the model due to
The effects of Aris. The adjusted model parameters sug-gested a
Received 19 June 2008 microfibrillated ‘‘simplified” composite structure with dense nanofiber
cellulose layers oriented in the plane of the film. Still, also
nanofibers from constraining effects on swelling from the high
Received in revised form 31 October 2008 Accepted 23 November 2008 Available online 3
wood on the modulus/hydrogen bonding cellulose network and reduced
December 2008
moisture sorption amylopectin molecular mobility due to strong starch–
kinetics (30% RH) cellulose molecular interactions were suggested to
of glycerol contribute to the reductions in moisture diffusivity.
plasticized and
Keywords: pure high-
amylopectin starch 2008 Elsevier Ltd. All rights reserved.
films were studied.
Nanocomposites C. Modelling Moisture diffusion
The presence of a
sivity glycerol plasticized high- temperature in a water formed during cellulose
propertie amylopectin starch, hereafter medium. The matrix biosynthesis in higher
s of referred to as amylopectin or AP, and reinforcement plants [6], whereas the
nanocom reinforced with different phases are both poly- microfibrillated
posites amounts of micro-fibrillated saccharides, where the cellulose nanofibers in
1. Introduction
are the cellulose nanofibers. This cellulose is the present study
interactio material has interesting nanostructured as in consists of aggregates
Nanocomposites, i.e. composites containing fillers ns plants. The matrix of microfibrils. The
that have at least one nanosized dimension, represent (includin phase is very soft with cellulose nanofibers are
a new class of materials that have interesting g nearly viscous behavior obtained by
penetrant diffusion properties [1–3]. The presence of aggregati and the mechanical disintegration of the
nanoparticles can significantly enhance the gas on) Corresponding author. Tel.: +46 8 790 material integrity plant fibre cell wall and
barrier, as was shown for polyimide films containing between 81 18; fax: +46 8 790 81 01. derives from the they typically have a
only 2 wt% clay [2]. The improved barrier was the cellulose nanofiber width and length of,
explained by the geometrical blocking due to the nanoparti network. Previous respectively, ca. 5–50
E-mail address: blund@kth.se (L.
wide impermeable clay platelets. Because of their cles.X studies on glycerol nm and several
small size, the surface-to-volume ratio of the Berglund).X plasticized starch microm-eters and they
nanoparticles is signifi-cantly greater than that of the materials, reinforced by have a high specific
corresponding microsized particles at the same mass 0266-3538/$ - see front matter 2008 cellulose nanofibers surface area [7]. In this
content [1,3]. Provided that strong particle–poly-mer Elsevier Ltd. All rights reserved. [4,5], have also shown study, the source of
The
molecular interactions exist, the smaller particles doi:10.1016/j.compscitech.2008.11.016 favourable interactions nanofibers was
present
have a greater ability to bond to the adjacent polymer between cellulose and bleached sulphite
paper
material, thereby reducing the chain segmental the polymer matrix. softwood cellulose pulp
reports
mobility and thus the penetrant dif-fusivity [3]. The Microfibril-lated that was disintegrated
the
presence of nanoparticles may also lead, in some cellulose (MFC) by combining mild
diffusion
cases, to a reduced chain packing adjacent to the filler mechanical properties [4] and nanofibers should not enzymatic hydrolysis
of
surface and thereby an increase in the free volume. mimics biological-plant be mistaken for with mechanical
moisture
This will then yield fas-ter solute diffusion through structures in several ways. microfi-brils. Cellulose shearing and high-
in pure
the interfacial particle–polymer layer [1]. Additional Processing is possible at room microfibrils are the 3– pressure
and
factors that are likely to be important for the diffu- 10 nm thick fibrils homogenization [8].
The cellulose nanofiber is a highly attractive organic interest. highly ordered extended chain diffraction provide non-cel-lulosic wood
biodegradable reinforcement in polymer The conformation. The general details of the crystal biopolymers at elevated
nanocomposites, due to its high aspect ratio, good poly-mer structure of cellulose has been structure [10,11]. The temperature, and the
inherent mechanical properties and its ability to form chains reviewed [9] and more recent pulping process structureX
a network [4,5]. The structure of the nanofibers is of are in studies based on neutron involves removal of
A.J. Svagan et al. / Composites Science and Technology 69 (2009) 500–506
501

days in a vacuum oven at 40 LC. expressed asX

Prior to testing, the dry specimens
of nanofibers from pulp has been studied [12]. Wood crystallites are very small
were stored in a dessicator with
ð1Þ
with typical crystallite dimensions of 4 nm (lateral) by 20 nm (length). The
cellulose aggregates making up the nanofibers have a typical lateral dimension drying agent.X
of about 15 nm. A significant portion of the chains are in a paracrystalline
extended chain conformation. X-ray diffraction data of the cellulose nanofiber in ¼ ox DðCÞ
2.2. Sorption measurements ox
the present study show an estimated degree of crystallinity of 66% [13] although
the distinction between crystalline and amorphous phase from the data is
somewhat ambiguous. Disordered regions are preferentially at aggregate A dynamic vapour sorption (DVS)
surfaces [14], and possibly also in localized amorphous re-gions along the chains apparatus from surface mea-surement
[9]. Such regions are expected to be accessible to water in contrast to the interior systems was used to determine the oC
of cellulose aggregates.X kinetics of water sorption. The
samples were exposed to air stream o
of a specific rel-ative humidity. The
Native starch consists of amylose and amylopectin. Both poly-mers are test specimens were thin (ca. 0.2
composed of a-D-glucose units, but amylose is a linear molecule whereas mm) rectan-gular films (ca 10 mm 7 oC
amylopectin is an extensively branched mac-romolecule. In the present study, mm). The specimens were thin
the starch is from potato tuber and contains predominantly amylopectin. The enough for the water diffusion to be
main disadvantage with starch materials is that they readily absorb water, which considered one-dimensional [20].
The thickness of the specimens was
significantly deteriorates their mechanical performance [5].X
measured at ambient condi-tions.
Each specimen was first dried in the
Diffusion of water in cellulose nanofiber reinforced starch com-posites was DVS cell until a constant weight was was solved for a film geometry,
reported in previous studies [5,15–17]. In these studies the moisture diffusivity attained and afterwards the relative where C, D and x are, respectively,
was considered to be constant, independent of moisture content. This is also humidity (RH) was rapidly raised the concentration and diffusivity of
assumed in the modelling of thermo-set based fiber composites [18]. However, from 0% to 30%. The temperature the diffusing solute and the
water vapour sorption in the present starch matrix systems necessitates inside the DVS was kept at 33 ± 0.5 coordinate in the thickness direction.
evaluation of more complex models. In fact, Russo et al. [19] showed that the LC. The weight of the specimen, At the outer boundary, a time-
moisture diffusivity in high-amylose starch, blended with a small amount of a inside the DVS, was measured every dependent ‘‘model” surface
water soluble polyol (1–10%), increased as an exponential function of the water minute. In order to make sure that concentration was used, simply as a
content. A moisture dependent diffusivity was therefore evaluated and 30% RH had been attained, the tool to account for the s-shape in the
implemented in the present study. The objective was to assess the effects of second weighing (i.e. the 1 min sorption curves [21,22]X
cellulose nanofibers on the moisture transport properties of amylopectin films. A value) was taken as the start of the
strong reduction in moisture dif-fusivity is observed and two different theoretical sorption experiment. The spec-imen
models are used to predict the reduction in zero-concentration moisture moisture uptake was calculated by C ¼ Ci þ ðC1 CiÞð1 e st
dividing the mass gain at steady state
diffusivity with increasing cellulose content.X Þ
with the dry weight. The theoretical ð2Þ
moisture uptake was calculated using
the rule of mixture, using the
moisture uptake at steady state of the
neat constituents as input.X where Ci and C1 are assumed to be,
respectively, an ‘‘initial” and a final
2. Experimental solute concentration and s is
considered as a surface ‘‘concen-
tration” relaxation time. For
2.1. Materials symmetry reasons, the concentration
2.3. Field-emission scanning electron
profiles were generated in only half
microscopy (FE-SEM)
Granular amylopectin potato starch with an amylose content lower than 1 wt% of the film cross-section and the
was kindly supplied by Lyckeby Stärkelsen (Kristianstad, Sweden). Cellulose inner boundary was consequently
nanofibers, in a 2 wt% water sus-pension, was kindly supplied by Professor Tom For micro-structural analysis, the treated as an isolated point. The
Lindström at STFI-Packforsk AB, Stockholm, Sweden. The preparation specimens were analyzed with a concentration-dependent diffusivity,
conditions of the present cellulose nanofibers was described in detail by Pääkkö Hitachi s-4300 field emission D(C), was here expressed as
et al. [8]. Bleached sulphite softwood cellulose pulp (Domsjö ECO Bright; scanning electron microscope (FE-
Domsjö Fabriker AB) consisting of 40 wt% pine (Pinus sylves-tris) and 60 wt% SEM). The specimens were fixed on a C
spruce (Picea abies) with a hemicellulose content of 13.8 wt% and a lignin a metal stub with carbon tape and DðCÞ ¼ DCOe D ð3Þ
content of 1 wt% was used as a source for the cellulose. The nanocellulose coated with gold using an Agar HR
suspension was prepared by treating the pulp in four steps; mechanical shearing, Sputter coater. An accelerating
enzymatic treatment, mechanical shearing and finally high-pressure voltage of 2 kV was used to obtain where DCO is the zero-concentration
homogenization. A microbiocide (5-chloro-2-ethyl-4-isothiazolin-3-one) was the secondary elec-tron images. diffusivity and aD is the plasti-
also added in order to avoid bacterial growth. The weight-average molec-X cization power. Although it might
have been possible to use other
relationships than that in Eq. (3), the
ular weight (MW ) of the cellulose was 200,000 g/mol. Glycerol (99% GC) and 3. Theory choice was motivated by pre-vious
work of Russo et al. [19], although,
drying agent (silica gel, SiO2) were purchased from Sigma– Aldrich.
in their case, the swelling was
significantly greater as compared to
The preparation of films was according to previous work [4]. The matrix in the the present case. The aver-X
plasticized films contained 50 wt% glycerol and 50 wt% amylopectin. The
nanocellulose content was varied from 0 to 70 wt% (cellulose/(cellulose +
amylopectin + glycerol)). Films were cut into test specimens and dried for two ot age diffusivity, D, was calculated as
Fick’s second law of diffusion [20],
 0

¼
1
Z C1 Eqs. (1)–(3) were numerically solved
DCOeaD C dC by using an implicit multi-step
ð4Þ C scheme described in detail by
Hedenqvist et al. [22,23], with a
nondimensional step change, dX, for
D
distance of dX = dx/l = 0.0057 (lX
1
502 A.J. Svagan et al. / Composites Science and Technology 69 (2009) 500–506
concentration-dependent diffusivity
is the half thickness of the film). The tolerance factor (tol) was set to 0.001, The composite the opposite was (aD – 0, continuos red lines),
calculations were performed with respect to the unit basic volume of the observed, i.e. the theoretical value described the data of the 40 (f) and
unswollen material, as described by Crank [20]. This reference system was was lower than the experimental 100 wt% (g) cellulose nanofiber
chosen because a zero volume change on mixing could not be assumed. The value. films relatively well, but not the data
of the neat amylo-pectin film (e).
diffusivities, including DCO,X None of the sorption curves could be
In Fig. 2 the experimental sorption described by the use of a constant
data and best fits using a con-stant
a

moisture diffusivity; a result

D and D, should be considered as approximate ‘‘apparent” param-eters; the (broken line) and a moisture probably due to that the dry AP
reasons are: (1) the concentration profiles were not determined explicitly, (2) the concentration-dependent diffu-sivity
matrix was in the glassy state at 33
error associated with the use of a numerical ‘‘finite difference” method (e.g. due (a – 0, continuos red line) are
D LC and there-fore significantly
to round-off effects) was neglected, (3) thermodynamic effects were not
shown. In Fig. 2a–d, the matrix mass plasticized by the sorbed water [4].
considered, (4) although the use of Eq. (2), in several cases, led to a very good
composition was 50/50 AP/glycerol As for the glycerol plasticized films,
fit to the sorption curves, the s-shape could possibly be described by other
and the cellulose nanofiber content all curves showed an s-shape. The
models/equations which are not, necessarily, describing only the surface
was varied between 0 and 70 wt%. origin of the s-shapes in Fig. 2a–g
conditions. Although, the fitting was carefully made, it cannot be guaranteed that
As observed, the curves in Fig. 2a–d was not explored explicitly here and
there are other solutions with equal or better fitting.X were s-shaped and the fit to the could be due to several factors, e.g.
experimental sorption data was swelling-induced compressive
successful, provided a time- surface stresses, a surface layer with
dependent surface concentration was different properties than those of the
used in addition to a concentration- interior [22] or instrument inertia.X
dependent diffusion coefficient
4. Results and discussion
[21,22,27]. For the neat matrix (a)
and the com-posite with 10 wt% In Table 2, parameter values used in,
Fig. 1a represents the surface of the 50 wt% nanocomposite film. The random cellulose nanofibers (b), also a or obtained from, the numerical fits
orientation and distribution of the nanofibers is appar-ent. The micrograph also constant moisture diffusivity to the experimental sorption data are
indicates some porosity. The thickness of most nanofibers was estimated to be generated good fits. This is probably presented. The surface concentration
30 ± 10 nm, although thicker entities are present. The typical nanofiber length is because the starch matrix contained a relaxation time s, is considered to
several mi-crons, resulting in a high aspect ratio. As a qualitative comparison, a large amount of glycerol, and was repre-sent the time needed for the
neat cellulose network film is shown in Fig. 1b. This is prepared in a different already from the start in a plasticized moisture surface concentration to
way, as described in [24]. However, the figure still serves as a good illustration state. The glass transition reach a steady state value and the
of a pure cellulose nanofiber network and the presence of porosity. X temperature of a 50/50 AP/glycerol plasticization power, aD, de-scribes
film is well below 33 LC [4]. Thus the increase of the diffusivity as a
the ‘‘extra” plasticising effect from function of the moisture
The moisture uptake decreased with increasing content of cel-lulose. Cellulose sorbed water was small. With 40 (c) concentration. Two data sets are
nanofibers are less hygroscopic than starch due to the higher degree of molecular and 70 wt% (d) cellulose nanofibers, presented for the 50/50 AP/glyc-erol
order. In cellulose, the disordered regions [9,14] are likely to be preferred good fits to the water sorption curves film and the 10 wt% MFC
sorption sites, as discussed in the introduction. Neat cellulose nanofiber films was obtained only with a use of a composite. These represent the best
sorbed only 40% and 56% of the amount of moisture sorbed in, respectively, the moisture concentration-dependent
plasticized and glycerol-free AP. The moisture/nanofiber film inter-actions are diffusivity. This indicated that, in this numerical fits using a constant (aD =
complex [25]. Since the relative humidity was low, moisture is not believed to be case, the plasticis-ing action of 0) and a moisture concentra-tion-
accumulated in the voids, see Table 1. The theoretical moisture uptakes obtained moisture played a more important dependent diffusivity (aD – 0). The
with the rule of mix-tures are reported in Table 1 for the nanofiber composites. role.X average and initial diffu-sion
For the glycerol plasticized composites, the theoretical moisture uptake data coefficients decreased with
were comparable to the corresponding experimental data at low MFC contents, increasing cellulose nanofiber
but significantly greater at 70 wt% MFC content. This could indicate that the content and increased with increasing
cellulose nanofiber network is reducing the swelling and thereby the moisture
In Fig. 2e–f, experimental and glycerol content. The latterX
uptake, similar to what was observed for natural rubber composites reinforced
modelled (best fits) sorption data are
with a network of chitin whiskers [26]. However, for the 40 wt% MFC, glycerol
shown for glycerol-free AP/cellulose
freeX nanofiber films. The mod-el, using a

Fig. 1. FE-SEM micrographs of the surface of (a) the 50 wt%

cellulose nanofiber reinforced composite (50/50
amylopectin/glycerol matrix) and (b) a neat cellulose film
(courtesy of M. Henriksson, Royal Institute of Technology). The
scale bars are (a) 3 lm and (b) 1.2 lm.

A.J. Svagan et al. / Composites Science and Technology 69 (2009) 500–506

503

q q
ct ce

100
Table 1

Moisture uptake, theoretical moisture uptake at 33 LC and 30% RH obtained from the rule of
mixture and void content for composites with varying cellulose nanofiber content and matrix MFC (wt%)
composition. Moisture
Theoretical
a
Void content (%) X
q
ct

uptake (%)
moisture
VV ¼

uptake (%)
50/50 Amylopectin/Glycerol matrix
a
Data obtained from Svagan et al. [4]. The
experimental density, qce, is an average of two
mercury displacement measurements. The
0 theoretical density, qct, is calculated from of
7.5 the densities of the constituents of the
– composite and their weight fractions. The
– densities of cellulose nanofibers, amylopectin
and plasticized amylopectin are assumed to be
3 3 3
1500 kg/m , 1260 kg/m and 1210 kg/m ,
respec-tively [4]. X
10
One specimen tested only.
7.1
7.0
0.3
was expected due to the plasticising
effects of glycerol on AP. How-ever,
it contradicted the results of Dufresne
et al. [5] which showed, on cellulose
40
nanofiber/potato starch composites,
5.5
5.7 the opposite relationship between the
– moisture diffusivity and the glycerol
content. Note that the unsatisfactory
numerical fitting to the experimental
data for neat amylopectin sample
resulted in an unusually high
70 relaxation time. Hence the parameter
3.9 values ob-tained in this numerical fit
4.4
7.3 should be treated with caution.X
The efficiency of the cellulose
nanofibers, in reducing the com-
posite moisture diffusivity, was
Amylopectin matrix probably somewhat reduced be-cause
the cellulose network introduced
some porosity in the nanocomposites
during the preparation stage [28], see
Table 1. Nevertheless, the moisture
zero-concentration diffusivity of the
10 wt% cellulose nanofiber film was
less than half of that of the
plasticized AP film. The pristine
cellulose network had a moisture
0 fitted to the present experimen-tal
zero-concentration diffusivity which
5.4
was less than 1% of the diffu-sivity
– requirement. The first model by Lord
– of the plasticized AP film. The
corresponding value, relative to the
glycerol-free AP film, was 15%.X
Generally, aD increases with
40
4.7 increasing crystallinity and
4.4 decreasing temperature [29], which
3.9 X
b indicates that it may be asso-ciated
with the polymer segmental/chain
mobility. In the present study aD
increased with increasing cellulose
content (Table 2). Two main reasons
100 were probable; (1) a reduced matrix
3.0 mobility due to interactions between
– individual nanofibers and AP [4]
24 and/or (2) a constrained swelling due
to the high-modulus nanofi-ber
network. When Tables 1 and 2 were
compared, it was apparent that aD
increased with decreasing solute
(moisture) saturation concentration.
This is commonly observed,
however, in the present case it was
not clear if the trend in aD reflected a
true physical phe-nomenon or was a
result from the numerical fitting
procedure.X
The model parameter, s, was
approximately the same for the
glycerol containing films with 10–70
wt% cellulose (aD – 0). If s is
associated with the decay of
swelling-induced stresses, it would
be expected to see it increasing with
increasing cellulose nanofiber
content. s would increase with a
decreasing chain mobility (polymer
relaxation rate) and moisture
diffusivity [21]. However, s
decreased with increasing glycerol
content (compare the data of the 40
wt% cellulose nanofiber films in Ta-
ble 2). The adjustable model
parameter Ci, relative to the final
concentration C1, was overall highest
for the glycerol-free films, a result
difficult to explain.X
In Fig. 3 normalized zero-
concentration diffusion coefficients
for glycerol containing films are
plotted as a function of the volumeX
fraction of cellulose. In Fig. 3a the
zero-concentration diffusivity values
were obtained using a concentration-
dependent diffusivity (aD – 0) and
this was also the case in Fig. 3b,
except for the 50/ 50 PAP/glycerol
film and the 10 wt% MFC composite
where the dif-fusivity data was
obtained using a constant diffusivity
(aD = 0) (Ta-ble 2). Most models that
incorporate a filler-induced
geometrical impedance do not predict
a zero diffusivity at 100% impenetra-
ble-filler content. The two models
data did, however, fulfil this
Raleigh [30] applies for composites
containing impermeable and infinite
cylindrical objects arranged in a
rectangular order and oriented
parallel to the composite surfaceX
DC
¼
1
/
5
DM
1
þ/
 a/ 4 a/
pa2 /
6 an aspect ratio of 0.5, which were
ðÞ
where DC is the diffusivity perpendicular to the cylindrical obstacles (cellulose
nanofibers) in the composite, DM is the diffusivity in the matrix (AP) and u is the
volume fraction of fibres. As observed in Fig. 3 this model could not predict the
relationship between the dif-fusivity and cellulose content.X
The second model fitted to the experimental data is due to Aris [31,32]. This
model applies to regularly spaced infinitely long flakes, which all have their
largest surfaces oriented parallel to the film surfaceX
DC
¼ with increasing cellulose nanofiber
where a is the flake aspect ratio; half
of the second largest flake dimension
1
divided by the smallest dimension. r
is the slit shape, i.e. half the slit
distance between two adjacent flakes
divided by the flake thickness, which
is also the slit height [33]. The
physical interpretation of each term
in the denominator on the right hand
side of Eq. (6) is as follows [32]: the
ðÞ unit term is merely the limit when the
flake content is zero, the second term
DM
corresponds to the diffusion
resistance due to the longer path
needed to circum-vent the flakes, the
1þ 1 /
þ
r p þ
1 /
third term represents the slit
ln h r ð 1 /Þi
resistance, which varies inversely
and directly with, respectively, the
slit width and slit height, the fourth
term describes the constriction of the
solute to pass into and out of the
narrow slit, also termed ‘‘necking”.
Although the nanofibers in this study
were not infi-nitely long flakes, it
2
a2/
was still interesting to see whether it
was possible to fit Eq. (6) to the
experimental data in Fig. 3a and b.
For ‘‘square fibers”, i.e. flakes with
regularly spaced in a hexagonal array
with a very small slit width (a slit
shape of 0.03), Eq. (6) could be
successfully fitted to the
experimental data in Fig. 3a. Hence,
the large decrease in dif-fusivity
should, according to the model, be
due, primarily, to the resistance of the
very narrow slits and the ‘‘necking”.
As observed in Fig. 3b, the model
could describe the trend in diffusivity
fairly well by considering flakes with
an aspect ratio of 2.2, and a slit shape
of 0.5. Hence, in this case the films
could be approximated as composites
with infinitely long flakes, in a
hexagonal array, where their width-
to-thickness ratio was almost 4.5 and
the thickness-to-slit-width ratio was
1. What is apparent from the fit-tings
(see Fig. 3a and b) is that the
reduction in moisture diffusiv-ity
content was faster than predicted by
simple models where the only
adjustable parameter is the volume
content (Lord Raleigh).X
The main reason for the observed
positive effects of MFC on the
transport/barrier properties is not
completely clear. The values ob-
tained for the adjustable parameters
in Eq. (6) corresponds to layers of
dense nanofiber systems aligned in
the plane of the film, sand-wiched
between AP layers or situated at the
film surface. The model is a highly
simplified description of the present
systems. Yet it is not entirely unlikely
that these high barrier layers may
exist. In essence,X
504 A.J. Svagan et al. / Composites Science and Technology 69 (2009) 500–506

a
1

b
1

increase

increase

0.8

0.8
mass
0.6

mass
0.6

Normalized
0.4
Normalized
0.4

0.2

Amylopectin/glycerol

0.2

(50/50)

10 wt% MFC

0
20
40
60
80
100
120

0
20
40
60
80
100
120

0
0

0.5 0.5
time (s )

0.5 0.5
time (s )

c
1

d
1
increase
0.8

increase
0.8

mass

mass

0.6

0.6

Normalized

Normalized

0.2
40 wt% MFC

0.2
70 wt% MFC

0.4

0.4

0
20
40
60
80
100
120

0
50
100

150
200
250

0.5 0.5
time (s )

0.5 0.5
time (s )

e
1

f
1
increase

increase

0.8

0.8

mass
0.6
mass
0.6

Normalized
0.4

Normalized
0.4

0.2

Amylopectin
0.2

40 wt% MFC

starch

0
50
100
150
200
250
300

0
50
100
150
200
250
300

0
 0.5 0.5
time (s )

0.5 0.5
time (s )

g
1

increase
0.8
mass

0.6

Normalized

0.2

100 wt% MFC

0.4

0
50
100
150
200
250
300

0
 0.5 0.5
time (s )

Fig. 2. Normalized mass increase [m(t)/m(1)] as a function of the square root of time for the neat cellulose nanofiber film (g) and the cellulose nanofiber composites with 50/ 50 amylopectin/glycerol
matrix (a)–(d) and amylopectin matrix (e)–(f). The continuos black line corresponds to experimental data obtained from DVS, the continuos red and broken lines are best fits obtained by the numerical
method for, respectively, aD – 0 and aD = 0. The cellulose contents are indicated in the figures. (For interpretation of the references in colour in this figure legend, the reader is referred to the web
version of this article.)
A.J. Svagan et al. / Composites Science and Technology 69 (2009) 500–506
505

Table 2
a s

3
The average (D) and zero-concentration diffusion coefficient values (D CO ), plasticization power ( D), surface concentration relaxation time ( ) and initially surface solute concentration in (g/cm )
normalized to the final concentration (Ci/C1) for composites with varying cellulose nanofiber content and matrix composition. Data is presented for numerical fits using a constant ( aD = 0) or a
moisture dependent diffusivity (aD – 0).

MFC (wt%)

9
2
1
DCO (10
9
2
1

aD (cm
3
g
1
s (s)
Ci/C1(–)

9
cm
2

s
1

DCO (10
9
cm
2

s
1

aD (cm
31
)

s (s)
Ci/C1 (–)

D (10

cm s
)

cm s
)

D (10

50/50 Amylopectin/glycerol matrix

0
51

39

7.6

313
0.08
62

62

417
0.08

10
34

18
13.5

244
0.1
47

47

400
0.07

40
15

5.1

27

238
0.14
–

–
–

70
5.3
1.9

36

250
0.17
–

–
–

Amylopectin matrix
0
3.0

2.2

8.5

11,100
0.57
–

–
–

40
2.2

0.72

32

1120
0.57
–

–
–

–
–

100
1.0

0.34

50

313
0.39
–

–
–
a
1

b
1

0.9

Exp data

0.9
Exp data

0.8

Raleigh

0.8

Raleigh
Aris, α = 0.5,

Aris, α = 2.2,

0.7

0.7

σ=0.03
σ = 0.5

M0
0.6

M0
0.6
/D
0.5

/D
0.5

C0
C0

0.4

0.4

D
D

0.3

0.3

0.2
0.2

0.1

0.1

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0

Nanofiber volume fraction, φ Nanofiber volume fraction, φ

Fig. 3. Experimental and calculated data (Models of Lord Raleigh [30] and Aris [31,32]) of the diffusion coefficient ratio, DC0/DM0, of cellulose nanofiber reinforced glycerol plasticized amylopectin
composites, where DC0 and DM0 are the zero-concentration diffusion coefficients for respectively, the composites and the matrix. In (a) the D C0 and DM0 values were obtained in the case of aD – 0 and
in (b) the values of DM0 and DC0 for 10 wt% cellulose nanocomposite were obtained for aD = 0. The DC0 values of other composites in (b) were obtained for aD – 0. The nanofibers are approximated

as impermeable to moisture. X
project (AS, MH) and by Dr. Mikael
Lindström STFI-Packforsk AB.
a layer structure could explain the trends in Fig. 3a and b, provided geometrical (70 wt% cellulose nanofibers)
Lyckeby Stärkelsen is acknowledged
impedance was the dominant effect. A layer structure, where the interlayer AP reduced the moisture uptake of the
for providing the amylopectin. The
material is free to swell in the thickness direction, would also explain the more composite to half the value of the
authors are grateful to Mikael
modest effect of MFC on the film saturation moisture content. In fact, a lamellar pure plasticized starch film. The
Ankerfors at STFI-Packforsk AB for
organization of cellulose nanofibers has been observed in a previous study [4] moisture sorption kinetics in the
skilled preparation of cellulose
for glycerol plasticized starch (50/50) composites reinforced with cellu-lose biomimetic nanocom-posites
nanofibers. The authors also thank
nanofibers. However, the layered structure could only be ob-served at high (cellulose nanofiber/plasticized
Tomas Larsson, STFI-Packforsk
contents [4,34]. At 10 wt% MFC content the cellulose nanofibers were amylopectin) must be de-scribed by a
A.B., for interesting discussions.
homogeneously distributed within the matrix. Nev-ertheless, there were moisture concentration-dependent,
probably additional factors contributing to the reduction in moisture diffusivity. rather than a constant diffusivity in
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The work was financed by the EU
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