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.
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], (0.99% sulfur on dry CNC). For all experiments deionized water
hydrochloric [30], phosphoric [31] or hydrobromic acid [32]. was used.
Combinations of acidic treatment and high-pressure homogeniza-
tion have also been reported [33,34]. Acid treatments remove the 2.2. Preparation of microfluidized MCC (F-MCC)
amorphous parts of cellulose leaving behind the highly crystalline
regions. Cotton [29], softwood [32], hardwood [35], sisal [36], bac- F-MCC was produced from a dispersion prepared with 0.3 kg of
terial cellulose [37], tunicates [38] and microcrystalline cellulose MCC in 1.5 kg of deionized water (20 wt.%), then stirred for 14 h at
(MCC) [39–41] have been frequently reported as starting materials room temperature. The dispersion was then fibrillated with a high
for the production of cellulose whiskers. pressure according to the setup previously described [17]. In par-
Increased attention has been given over the last decades to the ticular the 20% dispersion was pumped at 400 kPa through: (a)
study of polymers nanocomposites, containing mechanically two consecutive chambers of 400 and 200 lm (H230Z400lm and
strong fillers, such as clays, carbon nanotubes and silica, which H30Z200lm) for 3 passes; (b) two consecutive chambers of 200
are capable to improve the mechanical properties of neat polymers and 75 lm (H30Z200lm and H20Y75lm) for 7 passes. A defined
[42]. In a context of environmental preservation and optimization amount of water was added after each pass in order to decrease
of resources, the use of biobased cellulose nanofibers as reinforcing the viscosity of the suspension. After the first pass 400 mL of deion-
agents in composite materials has been widely reported [12]. ized water were added and then 150 mL after each pass. At the end
Elastic moduli of 150 GPa and 114 GPa have already been esti- of the mechanical treatment, the dispersion was stored at 4 °C and
mated for cellulose whiskers and the crystalline parts of nanofibr- the solid content determined by drying a known amount of disper-
illated cellulose, respectively [43,44]. Both types of nanofibers have sion into an oven at 105 °C until stable mass. The final solid content
been successfully employed with several polymers providing a was 10.9 wt.%.
valuable, but also renewable alternative to conventional fillers.
Some examples of polymer composites containing different types
2.3. Preparation of grinded MCC (G-MCC)
of whiskers or nanofibrillated cellulose, which showed improved
properties, are poly(styrene-co-butyl acrylate) [45], poly(caprolac-
G-MCC was produced starting from a dispersion prepared with
tone) [36,46], poly(vinyl acetate) [47] and hydroxypropylcellulose
1.3 kg of MCC in 8 kg of deionized water (16.3%), then stirred for
[17,48,49].
16 h at room temperature. The dispersion was then grinded follow-
Nevertheless, the production of cellulose whiskers by acid
ing previous processing conditions [18] with a Supermass Colloider
hydrolysis requires tedious neutralization steps that have so far
(MKZA10-20 J CE) from Masuko Sangyo Co. Ltd. (Kawaguchi/Saitam-
partially hindered the mass-scale production of these nanofibers.
a, Japan) equipped with non-porous grinding stones made of SiC/
Accordingly, in this paper we present the impact of different
Al2O3 particles in resin. The grinding stone rotated at ca.
mechanical treatments on commercially available MCC to produce
1500 rpm with a motor-load of 15 kW. The dispersion was passed
cellulose nanomaterials, as an alternative to the classical acidic
12 times through the grinder. 1 L of deionized water was added
process commonly reported for production of crystal-like material.
after each pass from pass 4 to pass 10 in order to decrease the vis-
We then evaluated the ability of the produced materials to rein-
cosity of the suspension (7 L of water total). After this mechanical
force hydroxypropylcellulose (HPC), a water soluble polymer
treatment the dispersion was stored at 4 °C and the solid content
matrix. Since our nanomaterials displayed stable suspensions in
determined by drying a known amount of dispersion into an oven
water, an improved dispersibility within the polymeric matrix
at 105 °C until stable mass. The final solid content was 8.7 wt.%.
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 2.4. Preparation of dry Hammer-milled MCC (H-MCC)
products in niche applications. A high shear homogenization pro-
cess involving a microfluidizer [48,49] and a grinding process using The dry milling of the MCC was performed using a Hammer
a Masuko Sangyo supermass colloider [18] have been evaluated in Witt-LAB (Frewitt SA, Fribourg, Switzerland) at hammer side using
this study, together with a dry hammer-milling treatment. All a screen ‘Chevron’ 0.2 mm at 7000 rpm. 7 consecutive cycles were
these methods have potential to be used in scale-up productions. operated in order to obtain finer particles (1 kg of MCC was milled
The obtained materials were characterized in terms of morphology in 42 s cycles).
and crystallinity. The composite films were prepared by a solvent
casting approach. The morphological and mechanical properties 2.5. Preparation of HPC composite films containing xMCC (x = F, G or
of the HPC composites were systematically evaluated using SEM, H) or commercial cellulose whiskers (W)
AFM, optical microscopy, sieve analysis and tensile test experi-
ments, respectively. The material produced by high-shear homog- Aqueous dispersions with a solid content of 3 wt.% HPC or
enization, grinding and hammer milled processes were 3 wt.% HPC and 5, 10 or 20 wt.% xMCC or whiskers (with respect
denominated F-MCC, G-MCC and H-MCC, respectively. Commer- to the 3 wt.% of polymer) were prepared by mixing a 7% HPC solu-
cially available whiskers were labelled W. 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
2. Experimental 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,
2.1. Materials respectively. The prepared mixtures were all treated with an Ika
ultraturrax system for 1 min at 8000 rpm, then heated and mag-
Microcrystalline cellulose Avicel Lattice NT 100 was purchased netically stirred for 30 min at 40 °C, left cooling to room tempera-
from FMC Biopolymer and hydroxypropylcellulose (HPC) with a ture and degassed under vacuum for 5 min. 55 g of each dispersion
weight-average molecular weight MW = 100,000 g mol 1 was pur- were poured into a silicon mold (15 18 cm) and the water was
chased from Sigma Aldrich. Commercially available cellulose left evaporating in a climatized room at 20 °C and 60% RH for
nanocrystals (herein referred to as whiskers, W) were purchased 5 days. The films were prepared in duplicate and had thicknesses
from the University of Maine Process Development Center from 50 to 70 lm.
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D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx 3
2.6. Scanning Electron Microscopy (SEM) between elongations from 0.05% and to 0.25%. The results pre-
sented are the mean values and the standard deviation of at least
SEM images were taken from samples of diluted 0.05 wt.% sus- 16–20 measurements.
pensions of which 2–3 drops were placed on a freshly cleaved mica
surface sample holder. All samples were sputter-coated directly 3. Results and discussion
with a platinum layer of about 7 nm (BAL-TEC MED 020 Modular
High Vacuum Coating Systems, BAL-TEC AG, Liechtenstein) in Ar The starting material selected for this comparative study was
as a carrier gas at 5 10 2 mbar. SEM images were finally recorded commercially available MCC because of its availability and low cost
with a FEI Nova NanoSEM 230 instrument (FEI, Hillsboro, Oregon, (64 $/kg vs. 1000 $/kg). The morphology of this crystalline material
USA) at an accelerating voltage of 5 kV and a working distance of has been evaluated by scanning electron microscopy (SEM). The
5 mm. SEM images reveal large particles with typical sizes below
120 lm (Fig. 1). This result has also been confirmed by sieve anal-
2.7. Atomic Force Microscope Imaging (AFM) ysis which yielded an average value of 108 lm (see Fig. S1).
AFM measurements were performed using atomic force micro- 3.1. Preparation of cellulose nanomaterials from MCC
scope (JPK instruments AG, Berlin, Germany) with a Nanowizard II
head and a SPM Controller III. A dilute drop of aqueous suspension A first product was obtained by mechanically treating MCC with
(0.01–0.1 mg ml 1) was dispersed on the freshly cleaved musco- the high shear homogenization process. An unusual high cellulose
vite mica disc surface (SPI Supplies, West Chester, Pennsylvania, concentration of 20 wt.% in water has been envisaged in our study.
USA, 9.9 mm diameter) mounted on the optical glass slide and This process is usually carried out at concentrations 10 times or
allowed to dry at 70 °C for an hour prior to analysis. AFM images more lower, both for the production of fibrils [17] and whiskers
were recorded in air with a silicon nitride cantilever tip (NANO [51]. The reason for this choice was that a higher concentration
WORLD, TESPA-50) in tapping mode with a spring constant of increases the viscosity of the dispersion, leading to higher shear
42 N/m at the resonance frequency of 320 kHz and a scan rate of stress on the MCC particles and the probability of friction forces
0.7 line s 1. Lengths and width reported in our study are the aver- between crystals. This was assumed to render the process more
age of 70 analyzed objects. efficient towards size reduction, but also to increase the output
2.9. Sieving
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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 The dry hammering process yielded an H-MCC material with
with larger particles in the micrometer range although our high reduced size compared to MCC but still in the micrometer length
concentration process seems more efficient than the previously range. From SEM images of MCC (Fig. 1) and H-MCC in Fig. 4b
reported one where the extent of size reduction seemed less effec- and Table 1, the width of the latter appears to be reduced but
tive [51]. not as much as after homogenization or grinding, and larger
The grinded material (G-MCC) presented a structure similar to objects are still present. This was confirmed by sieve analysis of
F-MCC with the presence of nanometer and micrometer sized par- the powders which resulted in the confirmation of size reduction
ticles (Fig. 4a), although in this case the smaller sized particles from an average of 108 lm for MCC to 59 lm for H-MCC (Fig. S1
seemed to be more abundant. 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 content of 5, 10 and 20 wt.% were produced by solvent casting.
commercially available whiskers were further accessed by Atomic Their properties were compared with HPC films reinforced with
Force Microscopy (AFM, Fig. 5). The average length and width mea- the same content of MCC and commercially available cellulose
sured for these materials are reported in Table 1. It is immediately whiskers (W).
noticeable that F-MCC contained nanometer-sized objects with a The morphology of the solvent-cast films has been analyzed
length of 416 ± 105 nm and a width of 8 ± 2 nm, similar to cellulose with optical microscopy (Fig. 6). The neat HPC film was transparent
whiskers already reported in the literature from the same source. as expected, except for small bubbles in the films, which could
The analysis of G-MCC, confirmed the presence of cellulose whis- have been formed during the film preparation by solution casting.
kers, which display lengths of 270 ± 80 nm and width of The nanocomposite films containing 10 wt.% of the various fillers
38 ± 9 nm, in agreement with previous observations of materials show well embedded filler particles within the polymer matrix
produced by sonication of MCC [40]. Commercially available whis- but the dispersion state was difficult to assess. Larger filler parti-
kers display lengths of 343 ± 93 nm and width of 51 ± 14 nm. cles are clearly distinguishable in the optical images for materials
From this morphological analysis, it appears that the homogeni- with larger particles such as MCC, H-MCC. The observed particles
zation process produced thinner fibers compared to the grinding, are smaller for F-MCC, G-MCC containing films and for W films
whereas lengthwise the two are similar. The hammer-milling, on they are not distinguishable because of the nanoscale dimensions
the other end, reduced the size of MCC but not to the same extent of this filler.
achieved for F-MCC and G-MCC. In general, it seems possible to tai- The mechanical properties of the composite films have been
lor the size reduction of MCC, based on the type of mechanical evaluated by tensile tests. The evolution of the tensile modulus
treatment. (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
3.4. Evaluation of the reinforcing potential of F-MCC, G-MCC and Table S1, S2 and S3 of the SI for detailed values).
H-MCC in HPC nanocomposites As it is well known that increased interfacial interaction
between the filler and the polymer matrix results in better
Although neither of the processes employed here completely mechanical performance [52–54], we expected this to favor the
disintegrates MCC to CNCs/whiskers, we speculate that the signif- interaction of our filler with HPC, because both materials are
icant content of CNCs/whiskers would render the products suitable hydrophilic and capable of hydrogen bonding.
as fillers. Hence, the reinforcing potential of F-MCC, G-MCC and H- Neat HPC films displayed a tensile modulus of 561 ± 30 MPa, a
MCC has been evaluated by preparing nanocomposites with tensile strength of 15.5 ± 0.7 MPa and a strain at break of
hydroxypropylcellulose (HPC). Thin films with cellulose nanofiller 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 7
4. Conclusions
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8 D. Bandera et al. / Reactive & Functional Polymers xxx (2014) xxx–xxx
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