Reactive & Functional Polymers xxx (2014) xxx–xxx

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Reactive & Functional Polymers

journal homepage: www.elsevier.com/locate/react

Influence of mechanical treatments on the properties of cellulose

nanofibers isolated from microcrystalline cellulose
Davide Bandera a,b, Janak Sapkota c, Sébastien Josset a, Christoph Weder c, Philippe Tingaut a, Xin Gao d,
E. Johan Foster c,e,⇑, Tanja Zimmermann a,⇑
a
Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Applied Wood Materials, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland
b
Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Bioactive Materials, Lerchenfeldstrasse 5, CH-9014 St. Gallen, Switzerland
c
Adolphe Merkle Institute, Polymer Chemistry and Materials, University of Fribourg, Rte de l’Ancienne Papeterie, CH-1723 Marly 1, Switzerland
d
Frewitt Fabrique des Machines SA, Case postale 615, 1701 Fribourg, Switzerland
e
Virginia Tech, Department of Materials Science & Engineering, 445 Old Turner Street, 213 Holden Hall, Blacksburg, VA 24061, USA

a r t i c l e i n f o a b s t r a c t

Article history: The possibility of preparing cellulose whiskers-like materials by mechanical treatment of commercially
Received 30 June 2014 available microcrystalline cellulose (MCC) was explored. High shear homogenization, grinding with a
Received in revised form 10 September supermass colloider, and hammer-milling were the processes selected to disintegrate the MCC, which
2014
yielded F-MCC, G-MCC and H-MCC, respectively. Processing aqueous dispersions with high solid content
Accepted 12 September 2014
Available online xxxx
allowed for the production of cellulose particles with greatly reduced dimensions. Morphological charac-
terization revealed that homogenization and grinding reduced the particle size more effectively than
hammer-milling, although the disintegration was incomplete in all cases. The reinforcing potential of
Keywords:
Microcrystalline cellulose
the materials was evaluated against commercially available whiskers by using the various particles as
Cellulose whiskers fillers to mechanically reinforce hydroxypropylcellulose. Nanocomposite films containing 5, 10, or
Mechanical treatments 20 wt.% of the filler were prepared and the mechanical properties were characterized. The results show
Film nanocomposites that H-MCCs are just slightly better than the original MCC, whereas F-MCC and G-MCC performed similar
Hydroxypropylcellulose to whiskers at 10 wt.% loading, despite the presence of a fraction of micrometer-sized particles. It is
therefore reasonable to envision the use of the more easily produced F-MCC and G-MCC as replacement
of cellulose whiskers in some applications.
Ó 2014 Published by Elsevier B.V.

1. Introduction Different treatments of native cellulosic materials have shown

Cellulose is among the most abundant biopolymers available on
earth [1] and can be found in plants, marine animals and bacteria
[2–6]. This biopolymer displays many desirable properties, includ-
ing biodegradability, renewability, high thermal stability, high
strength and extraordinary stiffness [7]. The chemical modification
of cellulose hydroxyl groups has facilitated the expansion of its
applications. It allows for the preparation of modified cellulosics
possessing improved properties and the ability to interact with
several other materials of various polarity [8]. Over the last
decades its use has been exploited particularly in applications
including paper, packaging films, pharmaceuticals, food and
textiles [9–11].
⇑ Corresponding authors. Tel.: +41 (0)26 300 9281; fax. +41 (0)26 300 96 24 (E.J.
Foster). Tel.: +41 (0)58 765 4115; fax. +41 (0)58 765 4007 (T. Zimmermann).
E-mail addresses: johan.foster@unifr.ch (E.J. Foster), tanja.zimmermann@empa.
ch (T. Zimmermann).
to be efficient in producing nanometer or micrometer sized fibers
[12–14]. Nanofibrillated cellulose (NFC), is obtained by disintegra-
tion [15] or refining [16] of cellulose fibers by mechanical
treatment, which is often combined with chemical or enzymatic
pre-treatments. This process affords water-dispersible and inter-
connected nanofibers with lengths in the micrometer range and
widths of usually above 10 nm. Many technologies have been
employed such as high shear homogenization and grinding
processes [17,18]. NFC can be produced from a wide range of cel-
lulose-based raw materials including wood [19–22], wheat straw
[23,24], bamboo [25,26], or aquatic weeds [27]. In these processes
both the amorphous and crystalline parts of cellulose are present
in the final products [13].
Cellulose whiskers, also referred to as cellulose nanocrystals
(CNCs) in the literature, on the other hand, are individualized
rod-like particles with aspect ratios between 10 and 100 and
diameters from 4 to 30 nm, and are in general much shorter than
micro- or nanofibrils [28]. They are usually produced by treating

http://dx.doi.org/10.1016/j.reactfunctpolym.2014.09.009
1381-5148/Ó 2014 Published by Elsevier B.V.

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2 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx
the cellulose source with strong acids such as sulfuric [29],
hydrochloric [30], phosphoric [31] or hydrobromic acid [32].
Combinations of acidic treatment and high-pressure homogeniza-
tion have also been reported [33,34]. Acid treatments remove the
amorphous parts of cellulose leaving behind the highly crystalline
regions. Cotton [29], softwood [32], hardwood [35], sisal [36], bac-
terial cellulose [37], tunicates [38] and microcrystalline cellulose
(MCC) [39–41] have been frequently reported as starting materials
for the production of cellulose whiskers.
Increased attention has been given over the last decades to the
study of polymers nanocomposites, containing mechanically
strong fillers, such as clays, carbon nanotubes and silica, which
are capable to improve the mechanical properties of neat polymers
[42]. In a context of environmental preservation and optimization
of resources, the use of biobased cellulose nanofibers as reinforcing
agents in composite materials has been widely reported [12].
Elastic moduli of 150 GPa and 114 GPa have already been esti-
mated for cellulose whiskers and the crystalline parts of nanofibr-
illated cellulose, respectively [43,44]. Both types of nanofibers have
been successfully employed with several polymers providing a
valuable, but also renewable alternative to conventional fillers.
Some examples of polymer composites containing different types
of whiskers or nanofibrillated cellulose, which showed improved
properties, are poly(styrene-co-butyl acrylate) [45], poly(caprolac-
tone) [36,46], poly(vinyl acetate) [47] and hydroxypropylcellulose
[17,48,49].
Nevertheless, the production of cellulose whiskers by acid
hydrolysis requires tedious neutralization steps that have so far
partially hindered the mass-scale production of these nanofibers.
Accordingly, in this paper we present the impact of different
mechanical treatments on commercially available MCC to produce
cellulose nanomaterials, as an alternative to the classical acidic
process commonly reported for production of crystal-like material.
We then evaluated the ability of the produced materials to rein-
force hydroxypropylcellulose (HPC), a water soluble polymer
matrix. Since our nanomaterials displayed stable suspensions in
water, an improved dispersibility within the polymeric matrix
has been expected. In particular, we compared the performance
of the materials we produced with regards to commercially avail-
able nanocrystals and possibly foresee the replacement of such
products in niche applications. A high shear homogenization pro-
cess involving a microfluidizer [48,49] and a grinding process using
a Masuko Sangyo supermass colloider [18] have been evaluated in
this study, together with a dry hammer-milling treatment. All
these methods have potential to be used in scale-up productions.
The obtained materials were characterized in terms of morphology
and crystallinity. The composite films were prepared by a solvent
casting approach. The morphological and mechanical properties
of the HPC composites were systematically evaluated using SEM,
AFM, optical microscopy, sieve analysis and tensile test experi-
ments, respectively. The material produced by high-shear homog-
enization, grinding and hammer milled processes were
denominated F-MCC, G-MCC and H-MCC, respectively. Commer-
cially available whiskers were labelled W.
2. Experimental
2.1. Materials
Microcrystalline cellulose Avicel Lattice NT 100 was purchased
from FMC Biopolymer and hydroxypropylcellulose (HPC) with a
weight-average molecular weight MW = 100,000 g mol 1 was pur-
chased from Sigma Aldrich. Commercially available cellulose
nanocrystals (herein referred to as whiskers, W) were purchased
from the University of Maine Process Development Center
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(0.99% sulfur on dry CNC). For all experiments deionized water
was used.
2.2. Preparation of microfluidized MCC (F-MCC)
F-MCC was produced from a dispersion prepared with 0.3 kg of
MCC in 1.5 kg of deionized water (20 wt.%), then stirred for 14 h at
room temperature. The dispersion was then fibrillated with a high
pressure according to the setup previously described [17]. In par-
ticular the 20% dispersion was pumped at 400 kPa through: (a)
two consecutive chambers of 400 and 200 lm (H230Z400lm and
H30Z200lm) for 3 passes; (b) two consecutive chambers of 200
and 75 lm (H30Z200lm and H20Y75lm) for 7 passes. A defined
amount of water was added after each pass in order to decrease
the viscosity of the suspension. After the first pass 400 mL of deion-
ized water were added and then 150 mL after each pass. At the end
of the mechanical treatment, the dispersion was stored at 4 °C and
the solid content determined by drying a known amount of disper-
sion into an oven at 105 °C until stable mass. The final solid content
was 10.9 wt.%.
2.3. Preparation of grinded MCC (G-MCC)
G-MCC was produced starting from a dispersion prepared with
1.3 kg of MCC in 8 kg of deionized water (16.3%), then stirred for
16 h at room temperature. The dispersion was then grinded follow-
ing previous processing conditions [18] with a Supermass Colloider
(MKZA10-20 J CE) from Masuko Sangyo Co. Ltd. (Kawaguchi/Saitam-
a, Japan) equipped with non-porous grinding stones made of SiC/
Al2O3 particles in resin. The grinding stone rotated at ca.
1500 rpm with a motor-load of 15 kW. The dispersion was passed
12 times through the grinder. 1 L of deionized water was added
after each pass from pass 4 to pass 10 in order to decrease the vis-
cosity of the suspension (7 L of water total). After this mechanical
treatment the dispersion was stored at 4 °C and the solid content
determined by drying a known amount of dispersion into an oven
at 105 °C until stable mass. The final solid content was 8.7 wt.%.
2.4. Preparation of dry Hammer-milled MCC (H-MCC)
The dry milling of the MCC was performed using a Hammer
Witt-LAB (Frewitt SA, Fribourg, Switzerland) at hammer side using
a screen ‘Chevron’ 0.2 mm at 7000 rpm. 7 consecutive cycles were
operated in order to obtain finer particles (1 kg of MCC was milled
in 42 s cycles).
2.5. Preparation of HPC composite films containing xMCC (x = F, G or
H) or commercial cellulose whiskers (W)
Aqueous dispersions with a solid content of 3 wt.% HPC or
3 wt.% HPC and 5, 10 or 20 wt.% xMCC or whiskers (with respect
to the 3 wt.% of polymer) were prepared by mixing a 7% HPC solu-
tion with the desired amount of xMCC or whiskers and deionized
water. F-MCC and G-MCC were used as aqueous dispersions as
obtained from mechanical treatment, whereas H-MCC and whisker
dispersions were prepared by ultrasonicating for 2 min (10 s ON-
10 s OFF cycles at 10% power) a 3.8 wt.% and a 0.8 wt.% suspension,
respectively. The prepared mixtures were all treated with an Ika
ultraturrax system for 1 min at 8000 rpm, then heated and mag-
netically stirred for 30 min at 40 °C, left cooling to room tempera-
ture and degassed under vacuum for 5 min. 55 g of each dispersion
were poured into a silicon mold (15  18 cm) and the water was
left evaporating in a climatized room at 20 °C and 60% RH for
5 days. The films were prepared in duplicate and had thicknesses
from 50 to 70 lm.
 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx 3

2.6. Scanning Electron Microscopy (SEM)
SEM images were taken from samples of diluted 0.05 wt.% sus-
pensions of which 2–3 drops were placed on a freshly cleaved mica
surface sample holder. All samples were sputter-coated directly
with a platinum layer of about 7 nm (BAL-TEC MED 020 Modular
High Vacuum Coating Systems, BAL-TEC AG, Liechtenstein) in Ar
as a carrier gas at 5  10 2 mbar. SEM images were finally recorded
with a FEI Nova NanoSEM 230 instrument (FEI, Hillsboro, Oregon,
USA) at an accelerating voltage of 5 kV and a working distance of
5 mm.
2.7. Atomic Force Microscope Imaging (AFM)
between elongations from 0.05% and to 0.25%. The results pre-
sented are the mean values and the standard deviation of at least
16–20 measurements.
3. Results and discussion
The starting material selected for this comparative study was
commercially available MCC because of its availability and low cost
(64 $/kg vs. 1000 $/kg). The morphology of this crystalline material
has been evaluated by scanning electron microscopy (SEM). The
SEM images reveal large particles with typical sizes below
120 lm (Fig. 1). This result has also been confirmed by sieve anal-
ysis which yielded an average value of 108 lm (see Fig. S1).

AFM measurements were performed using atomic force micro-
scope (JPK instruments AG, Berlin, Germany) with a Nanowizard II
head and a SPM Controller III. A dilute drop of aqueous suspension
(0.01–0.1 mg ml 1) was dispersed on the freshly cleaved musco-
vite mica disc surface (SPI Supplies, West Chester, Pennsylvania,
USA, 9.9 mm diameter) mounted on the optical glass slide and
allowed to dry at 70 °C for an hour prior to analysis. AFM images
were recorded in air with a silicon nitride cantilever tip (NANO
WORLD, TESPA-50) in tapping mode with a spring constant of
42 N/m at the resonance frequency of 320 kHz and a scan rate of
0.7 line s 1. Lengths and width reported in our study are the aver-
age of 70 analyzed objects.
3.1. Preparation of cellulose nanomaterials from MCC
A first product was obtained by mechanically treating MCC with
the high shear homogenization process. An unusual high cellulose
concentration of 20 wt.% in water has been envisaged in our study.
This process is usually carried out at concentrations 10 times or
more lower, both for the production of fibrils [17] and whiskers
[51]. The reason for this choice was that a higher concentration
increases the viscosity of the dispersion, leading to higher shear
stress on the MCC particles and the probability of friction forces
between crystals. This was assumed to render the process more
efficient towards size reduction, but also to increase the output

2.8. Optical microscopy

Optical microscopy analyses were performed using Olympus

BX51 (Olympus Corporation) on samples of 20–30 lm thick films.
Each film was mounted on a glass microscopy slide and the images
were recorded with an objective lens of 50x magnification
equipped with DP72 digital camera.

2.9. Sieving

Sieve analysis was performed using Retsch Analytical Sieve

Shaker AS 200 Control for 30 g of each samples with a vibration
rate of 2 min and amplitude of 2 mm g 1. Vulkollan cubes were
added as sieving aid.

2.10. X-ray diffraction

The XRD measurements were performed with a Bruker D8

Advanced Diffractometer (Cu Ka radiation, k = 1.54184 Å), tube
parameters: V = 40 kV, I = 40 mA, using a parallel incident beam
prepared by a Göbel X-ray mirror. The patterns were recorded with
Fig. 1. Scanning electron microscopy image of commercially available MCC.
a 1D position sensitive detector (VÅNTEC). The samples were
investigated in h/2h mode using a rotating disk-shaped sample
holder (rotated at 15 rpm) on which the sample was spread to form
a flat surface. The scans were recorded in the angular range from
5 < 2h < 90° with a step width of D2h = 0.015° at a speed of
5° min 1, respectively. The data have been analyzed using Micro-
soft excel according to the peak height method [50].

2.11. Tensile testing

For each nanocomposite film composition 10 to 12 dog-bone

shaped specimens were cut of (length 5 cm, surface 330 mm2,
width of the central part 4 mm). They were allowed to equilibrate
for 48 h at 23 °C and 50% RH before measurement. The mechanical
properties in tension were determined using a Zwick Z010/TH2A
(Zwick GmbH & Co. KG, Ulm, Germany): the pre-load applied
was 0.2 N, the loading speed 10 mm min 1 on a 100 N loading cell.
The tensile modulus (E) was determined using the strain curve Fig. 2. X-ray diffractograms plot of MCC, G-MCC, F-MCC, H-MCC and W.

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4 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx

of the product. A significant increase in the suspension viscosity Hammer-milling of MCC was performed for one kg of starting
was noticed after only 3 passes. Remediation to this issue, which MCC in the dry state affording powder particles of reduced diame-
made the process more difficult due to the lower flow rate, con- ter in every consecutive step of 7 cycles. No heating of the product
sisted in the addition of a defined volume of water after each pass was observed during milling and hence no cooling medium was
and proceeding with the homogenization treatment for 10 passes. used. The final average particle size was determined to be 59 lm
The final product (F-MCC) had a concentration of 10.9 wt.%. according to sieve analysis (Fig. S2).
The grinding treatment of MCC with the Masuko Sangyo super-
mass colloider [18] was performed starting with a 16.3 wt.% cellu-
3.2. Crystallinity analysis
lose suspension in water, which was gradually introduced into the
equipment and the material was mechanically grinded through
The X-ray diffraction patterns of MCC and the products
two rotating disks having an estimated clearance of 100 lm. Dur-
obtained by the different mechanical treatments are presented in
ing this treatment, the problematic increase of the suspension vis-
Fig. 2. The crystallinity index (CI) of each material is reported in
cosity was also addressed by adding a defined volume of water
Table 1. A CI of 91% has been measured for the original MCC, which
after each pass. The final dispersion (G-MCC) had a concentration
is in agreement with other studies reported in the literature [41].
of 8.7 wt.%.
Similar CIs have been calculated for all treated materials, which
suggests that the crystal structure of MCC was not affected by
Table 1
Summary of crystallinity and size measurements for the processed materials. the strong mechanical treatments used in our study. Commercially
available cellulose whiskers displayed also a CI similar to the origi-
Material CIa Length Width
nal MCC and the other materials produced.
MCC 84 – 108 lmc
F-MCC 90 416 ± 105 nmb 8 ± 2 nmb
G-MCC 82 270 ± 80 nmb 38 ± 9 nmb 3.3. Morphological characterization of mechanically treated MCC
H-MCC 82 – 59 lmc
W 79 343 ± 93 nmb 51 ± 14 nmb
The morphology of the mechanically treated MCC has been
a
Crystallinity index determined by XRD. evaluated by SEM. A substantial size reduction can be observed
b
Determined by AFM. for F-MCC (Fig. 3) after the homogenization treatment as compared
c
Determined by sieve analysis as diameter. with the starting material, but the material was not homogeneous.

Fig. 3. Scanning electron microscopy images of (a) F-MCC deposited from a 0.05 wt.% aqueous dispersion and (b) a magnification of the area marked with the white square.

Fig. 4. Scanning electron microscopy images of (a) G-MCC and (b) H-MCC deposited from a 0.05 wt.% aqueous dispersion.

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 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx 5

The disintegrated F-MCC displayed cellulosic nanocrystals together
with larger particles in the micrometer range although our high
concentration process seems more efficient than the previously
reported one where the extent of size reduction seemed less effec-
tive [51].
The grinded material (G-MCC) presented a structure similar to
F-MCC with the presence of nanometer and micrometer sized par-
ticles (Fig. 4a), although in this case the smaller sized particles
seemed to be more abundant.
The dry hammering process yielded an H-MCC material with
reduced size compared to MCC but still in the micrometer length
range. From SEM images of MCC (Fig. 1) and H-MCC in Fig. 4b
and Table 1, the width of the latter appears to be reduced but
not as much as after homogenization or grinding, and larger
objects are still present. This was confirmed by sieve analysis of
the powders which resulted in the confirmation of size reduction
from an average of 108 lm for MCC to 59 lm for H-MCC (Fig. S1
and Fig. S2 in the SI).

500 nm 500 nm

500 nm 500 nm

500 nm 500 nm

1
Fig. 5. Height (left) and phase (right) atomic force microscopy images of (a) F-MCC, (b) G-MCC, and (c) commercial whiskers deposited from a 0.01–0.1 mg ml aqueous
dispersion.

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6 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx

The dimensions of smaller crystals found in F-MCC, G-MCC and
commercially available whiskers were further accessed by Atomic
Force Microscopy (AFM, Fig. 5). The average length and width mea-
sured for these materials are reported in Table 1. It is immediately
noticeable that F-MCC contained nanometer-sized objects with a
length of 416 ± 105 nm and a width of 8 ± 2 nm, similar to cellulose
whiskers already reported in the literature from the same source.
The analysis of G-MCC, confirmed the presence of cellulose whis-
kers, which display lengths of 270 ± 80 nm and width of
38 ± 9 nm, in agreement with previous observations of materials
produced by sonication of MCC [40]. Commercially available whis-
kers display lengths of 343 ± 93 nm and width of 51 ± 14 nm.
From this morphological analysis, it appears that the homogeni-
zation process produced thinner fibers compared to the grinding,
whereas lengthwise the two are similar. The hammer-milling, on
the other end, reduced the size of MCC but not to the same extent
achieved for F-MCC and G-MCC. In general, it seems possible to tai-
lor the size reduction of MCC, based on the type of mechanical
treatment.
3.4. Evaluation of the reinforcing potential of F-MCC, G-MCC and
H-MCC in HPC nanocomposites
Although neither of the processes employed here completely
disintegrates MCC to CNCs/whiskers, we speculate that the signif-
icant content of CNCs/whiskers would render the products suitable
as fillers. Hence, the reinforcing potential of F-MCC, G-MCC and H-
MCC has been evaluated by preparing nanocomposites with
hydroxypropylcellulose (HPC). Thin films with cellulose nanofiller
content of 5, 10 and 20 wt.% were produced by solvent casting.
Their properties were compared with HPC films reinforced with
the same content of MCC and commercially available cellulose
whiskers (W).
The morphology of the solvent-cast films has been analyzed
with optical microscopy (Fig. 6). The neat HPC film was transparent
as expected, except for small bubbles in the films, which could
have been formed during the film preparation by solution casting.
The nanocomposite films containing 10 wt.% of the various fillers
show well embedded filler particles within the polymer matrix
but the dispersion state was difficult to assess. Larger filler parti-
cles are clearly distinguishable in the optical images for materials
with larger particles such as MCC, H-MCC. The observed particles
are smaller for F-MCC, G-MCC containing films and for W films
they are not distinguishable because of the nanoscale dimensions
of this filler.
The mechanical properties of the composite films have been
evaluated by tensile tests. The evolution of the tensile modulus
(E), tensile strength (r) and strain at break (e) as a function of filler
content is shown for the various materials in Fig. 7 (see also
Table S1, S2 and S3 of the SI for detailed values).
As it is well known that increased interfacial interaction
between the filler and the polymer matrix results in better
mechanical performance [52–54], we expected this to favor the
interaction of our filler with HPC, because both materials are
hydrophilic and capable of hydrogen bonding.
Neat HPC films displayed a tensile modulus of 561 ± 30 MPa, a
tensile strength of 15.5 ± 0.7 MPa and a strain at break of
29.1 ± 4.1%. The introduction of MCC provoked a negligible

a b

c d

e f

Fig. 6. Optical micrographs of selected nanocomposite films containing hydroxypropylcellulose (HPC) and 10 wt.% of the nanocellulose filler: (a) commercial MCC, (b) F-MCC,
(c) G-MCC, (d) H-MCC, (e) whiskers and (f) Neat HPC (scale bars = 0.5 lm).

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 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx
Fig. 7. Graphs show: (a) the evolution of the tensile modulus (E), (b) tensile
strength (r) and (c) strain at break (e) for HPC nanocomposites reinforced with G-
MCC, F-MCC, H-MCC and W as function of the filler content.
increase of E but a sharp decrease in tensile strength, which might
be associated with an inhomogeneous dispersion of the filler in the
composite materials or the formation of a weak MCC-HPC
interface.
A gradual increase of E has been noted upon the increase of G-
MCC, F-MCC and H-MCC contents in the HPC matrix, as expected,
which reflected a gradual increase of the composites stiffness.
Hence, the cellulosic particles display a higher stiffness than the
soft HPC polymeric material. Notably, E in F-MCC and G-MCC nano-
composites show similar behavior and the reinforcing effect at 10%
is indistinguishable from that of the whisker nanocomposites.
Lower E values were noted for composites reinforced with
H-MCC and levelling off effect has been observed above 10 wt.%
of filler content, which was possibly due to the larger particles as
well as a filler aggregation, respectively [36,55].
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7
Furthermore, differences in reinforcing potential have been
noticed between these fillers. A progressive increase in r has been
observed for HPC reinforced with G-MCC and F-MCC with increas-
ing filler loadings, while no evolution was seen for H-MCC. These
differences have been attributed to the higher aspect ratios of
G-MCC and F-MCC compared to H-MCC, as well as the possibility
of nanoparticles percolation/interaction within the polymeric
matrix. These results are in agreement with the particles morpho-
logical differences discussed previously and the confirmed
presence of nanometer scale objects in G-MCC and F-MCC.
Interestingly, a similar reinforcing potential has been observed
for G-MCC and F-MCC, with maximum r values reaching
24.5 ± 2.5 MPa and 25.4 ± 2.4 MPa for 20 wt.% of fillers, respec-
tively, in line with other works where maximum improvement
was observed with 20 wt.% of filler [17,48]. This observation sug-
gests that although G-MCC has a significantly larger diameter
and their length is comparable to F-MCC, in the end this difference
does not affect the reinforcing power displayed, which is analo-
gous. According to percolation theory, the threshold for these
types of filler can be calculated with the simplified formula
mc  [0.7/(L/d)] 100 where L and d are the length and the width
of the particles, respectively (considering only the fraction of mate-
rial having whisker-like size) [28]. It turns out that for F-MCC and
G-MCC the threshold would be 1.3% and 9.8% respectively. These
values fit well with our results for which we observe a more
modest increase of E for F-MCC and G-MCC with respect to the fil-
ler loading. For 5 wt.% our results agree with a previous report [49].
HPC composites reinforced with W displayed higher E and
r than any other materials for 5 wt.% and 20 wt.% filler content,
but similar to F-MCC and G-MCC at 10 wt.%. These results highlight
the potential of F-MCC and G-MCC in composite applications and
represent a viable alternative to cellulose whiskers prepared with
strong acidic conditions.
For all composites in this study, a typical decrease of e has been
noted with the filler content, as already reported for composite
materials reinforced with cellulose particles.
4. Conclusions
Mechanical treatments of MCC offer the possibility to reduce
the particle size of this highly crystalline cellulosic material. All
methods used here potentially allow for easy and high-throughput
production of materials with a method-dependent fraction and
morphology of nanoparticles. Hammer-milling affords H-MCC,
which is mainly composed of low-aspect-ratio particles. Homoge-
nization produces F-MCC with long and thin fibers, whereas grind-
ing affords G-MCC with particles that feature a similar length but a
larger diameter. Despite this size difference, F-MCC and G-MCC
display a similar reinforcing behavior in HPC films for a range of fil-
ler loadings. Well-defined whiskers, which were used as reference,
have a higher reinforcing capability than any of the MCC-based
materials at low and high filler content, but G-MCC and F-MCC
reinforced composites match the properties of whisker-reinforced
HPC at a filler content of 10 wt.%. Thus, even though the mechani-
cal treatments afford cellulosic materials that are comprised of
mixtures of nano- and microparticles, this distribution does, at
least not in the HPC composites studied here, significantly limit
the reinforcing capability in comparison to well-defined whiskers.
On the other hand, for use in optical applications a better disinte-
gration may be required.
Acknowledgments
We thank Dr. Arndt Remhof for helping with XRD data acquisi-
tion and Ms. Esther Strub for tensile testing, both at the Swiss
8 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx
Federal Laboratories for Materials Science and technology. The
authors gratefully acknowledge financial support from the Swiss
National Science Foundation (NRP66: Resource Wood, Nr.
406640_136911/1) and the Adolphe Merkle Foundation.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.reactfunctpolym.
2014.09.009.
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