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Powder Technology
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a r t i c l e
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Article history:
Received 2 January 2014
Received in revised form 30 March 2014
Accepted 4 April 2014
Available online 15 April 2014
Keywords:
Cellulose nanocrystal (CNC)
Porous powder structure
Melt dispersion
Polymer nanocomposite
a b s t r a c t
The microstructure of CNC particles depends strongly on the drying method employed during manufacturing.
The effect of different drying techniques, including spray drying, freeze drying, and spray freeze drying (SFD),
on microstructure of cellulose nanocrystal (CNC) particles was studied. Conventional drying methods (i.e. spray
and freeze drying) yielded packed and dense agglomerates of CNC. Capillary forces and ice crystal growth play
key roles in CNC aggregation during spray and freeze drying, respectively. It was found that, in the absence of
these forces, in the SFD technique, the dispersed state of CNC in water could be frozen in. Thus, SFD of CNC suspension resulted in a powder with porous structure. A lament-like agglomerate structure consisting of nanobers was formed at low CNC concentrations (ca. b2 wt.%), while a spherical foam structure was obtained at
higher CNC concentrations. Polypropylene (PP) nanocomposites containing spray dried CNC, freeze dried CNC,
and spray freeze dried CNC (CNCSFD) were prepared via melt mixing in an internal batch mixer. Optical light
and scanning electron microscopy coupled with rheological properties showed better dispersion of CNCSFD
agglomerates. Moreover, PP samples containing CNCSFD showed signicant increases in mechanical properties.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Cellulose nanocrystals (CNCs) are obtained by strong acid hydrolysis
or oxidation of cellulose crystals from cellulose microbrils in forest
products and/or other sources [1,2]. CNC particles have been of growing
interest because they are biocompatible and biodegradable and can be
obtained from a variety of natural sources. Furthermore, the physical
and mechanical properties of CNC make it a potential candidate for reinforcement of polymers [3,4].
CNC nanoparticles have high specic surface area and surface energy. Consequently, they aggregate and form larger particles during and/
or in the last step of the production process. After separation from
other impurities and amorphous cellulose, CNC is obtained as an aqueous suspension. However, there are a variety of applications where CNC
is needed in the powder form. Such applications include the preparation
of polymeric nanocomposites in hydrophobic polymer matrices using
melt processing. Moreover, transportation of CNC in the powder state
reduces transportation costs. Therefore, a drying step is required to obtain dry CNC powder from the aqueous suspension. For CNC aqueous
suspension, conventional drying methods such as spray and freeze drying have been employed [5,6]. In the spray drying method, CNC suspension is atomized inside a drying chamber where hot air (higher than
100 C) is used as the drying atmosphere which results in a powder
with particle sizes in micron size range. Freeze drying or lyophilization
Corresponding author.
E-mail address: musa.kamal@mcgill.ca (M.R. Kamal).
http://dx.doi.org/10.1016/j.powtec.2014.04.016
0032-5910/ 2014 Elsevier B.V. All rights reserved.
AH 24D0
where D0 and are the theoretical molecular distance between two particles in contact, known as cutoff, 0.165 nm, and surface energy of CNC
at 190 C [21], respectively.
The inter-particle van der Waals interaction energy and force between nanoparticles depend on the orientation of the individual nanoparticles. Inter-particle energy of two parallel and cross cylinders is
comparable to or stronger than inter-molecular energy such as hydrogen bond energy (3.48 10 20 J) and C\C covalent bond energy
(5.98 10-19 J) [23]. It is also noteworthy that CNC nanoparticles can interact via hydrogen bonding. The number of hydroxyl groups per unit
surface area (7.2 OH/nm2) was calculated based on CNC unit cell. Also,
the hydrogen bonding interaction energy associated with the hydroxyl
groups on the CNC surface for two CNC nanoparticles in contact with
parallel orientation (Table 1) is estimated to be 7.5 1016 J [4]. This interaction energy is almost two orders of magnitude higher than van der
Waals colloidal energy. However, hydrogen bonding energy interactions are short range (less than 0.32 nm) compared to the longer
range colloidal van der Waals energy (up to 100 nm). At very small
inter-particle distance, hydrogen bond interaction is predominant, but
at higher separation distance, the major interaction energy is due to colloidal van der Waals interactions. CNC surface modication (covalent
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and non-covalent methods) is employed to overcome hydrogen bonding interactions and thus to improve CNC dispersion in polymer matrices. Modiers could also increase inter-particle distance between CNC
nanoparticles. Thus, according to Table 1, van der Waals interactions become lower. Unlike interaction energy, the force required to separate
nanoparticles depends on the path or method of separation [24]. In
the case of cylindrical shape nanoparticle (CNC in this work), the orientation of nanoparticles in the ow eld determines ease or feasibility of
separation.
CNC nanoparticles with parallel orientation can be separated in two
ways: pulling and peeling (Fig. 1). In the pulling mechanism, the separation route is perpendicular to the surface. In fact, contact area is constant but the equilibrium distance gradually increases. Therefore, the
required hydrodynamic force to fully separate two parallel CNC particles is 115 nN (see Table 1). The pulling mechanism is very fast and
rapid. It is known in dispersion literature as the breakup/rupture mechanism (discussed later). However, in the case of peeling, the applied
force is spent on reducing contact area between the two parallel CNC
nanoparticles. Thus, the force required to fully separate the CNC particles is much less than the pulling force:
F peeling
U plate
12
7:6 10 N:
L
Table 1
Inter-particle interaction energy and force between two cross and parallel CNC cylindrical
particles [21,32].
Force and energy
equations
0:5
L
HR
U parallel A24z
1:5
F parallel
Particle
geometry
Inter-particle
energy
(J) (at 190 C)
Inter-particle
force
(N) (at 190 C)
1.231017
1.15107
1.11018
1.27109
0:5
AH R L
16z2:5
HR
U cross A6z
F cross A6zH 2R
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between hydrodynamic forces (Fh) and cohesive forces (Fc) [27]. Rheological properties of the polymeric matrix and the design and operating
conditions of mixing equipment or the ow eld determine the hydrodynamic forces.
It is possible to estimate the cohesion strength of agglomerated
nanoparticles from forces of attraction between two isolated nanoparticles in contact. Chemical composition, surface properties of ller, packing structure, and size of particle determine the strength of the
agglomerated structure. The strength of an agglomerate, , can be estimated using Rumpf's equation [28]:
1 F
a2
1 AH R0:5 L
:
16a2 z2:5
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Fig. 4. AFM topography a) height, b) phase and c) a typical example of size measurements for three labeled CNC (as received).
was freeze dried using freeze dryer equipment (Labconco 2.5 L). For
spray freeze drying, an aqueous CNC suspension was sprayed into a container containing liquid nitrogen, equipped with a magnetic stirring bar,
and then transferred to the freeze dryer equipment (Labconco 2.5 L).
The frozen suspension was lyophilized at 52 C and 0.05 mbar for a
period of time (2472 h).
3.3. Preparation of polymer/CNC nanocomposite
Melt compounding was conducted in an internal batch mixer
(Rheocord 9000, Haake). The internal batch mixer operates with two
blades (roller blades) in counter rotating conguration and total capacity of 60mL. Compounding was carried out at 190 C and 60 rpm rotor
speed for 10 min, under nitrogen atmosphere. CNC powder was prepared using different drying techniques. As received, freeze dried, and
spray freeze dried CNC were fed into internal batch mixer after polymer
granules were melted. Finally, the mixture was collected for further
characterization after cooling to room temperature.
3.4. Characterization
3.4.1. Morphological studies
The size and shape of the CNC nanoparticle agglomerates (as received) were examined using transmission electron microscopy (TEM)
(Philips CM200, 200 kV). A drop, 510 L, of aqueous CNC suspension
(0.01 wt.%) was deposited on a carbon-coated copper grid. After evaporation of water, a drop of uranyl acetate water solution (2 wt.%) was deposited on the same grid in order to stain CNC particles.
Atomic force microscopy (AFM) was used to determine the shape and
size of CNC nanoparticle agglomerates (as received). A drop, ca. 5 L, of
0.1% w/v solution of poly-L-lysine was placed on a piece of freshly cleaved
mica for 2 min, and then rinsed with water. Subsequently, the mica was
Fig. 5. SEM image (left) and crossed light microscopy (right) of spray dried CNC
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Fig. 6. SEM image (left) and PLM image (right) of freeze dried CNC
dipped and held for 20 s in the CNC suspension. Then, it was rinsed with
distilled water and dried overnight. The AFM images were obtained under
ambient conditions using a Multi-mode Nanoscope IIIa with Extender
(Digital Instrument, Santa Barbara, CA). Height and phase images
were acquired in tapping mode using etched silicon cantilevers
with 42 N m 1nominal spring constant, 285 kHz nominal resonance
frequency, and b10 nm nominal tip radius (Nanoworld, USA). Software
Nanoscope Analysis 1.4 (Bruker, Santa Barbara, CA, USA) was used to
process the AFM images (512 512 pixels).
The surface topography of CNC powder obtained by different drying
methods was examined, using eld emission scanning electron microscopy (FE-SEM, Hitachi S-4700) operated at 2 kV. Prior to SEM observation, CNC powders were coated with goldpalladium vapor deposition
for a period of 30 s.
The cryo-fractured surface of PP samples was coated with gold vapor
and observed under SEM (JSM-7400F, JEOL, Japan) to evaluate the distribution of CNC in the PP matrix.
Morphology of CNC powder and polymer nanocomposite samples
was directly observed by an upright polarized light microscopy (PLM),
BX50 (Olympus, Japan), where a light source passes through a polarizer,
compensator of 530 nm, sample and then a cross analyzer. The compensator is inserted between polarizer and analyzer to make better contrast. Polymer/CNC samples were molded with a Carver hot press
(Wabash, IN, USA) to make a thin lm with 1015 m thickness.
Fig. 7. SEM image of CNCSFD0.5 (left) and CNCSFD1 (right) at low (a and c) and high (b and d) magnications.
293
Fig. 8. SEM image of CNCSFD2 (left) and its interior structure (right) at low (a and c) and high (b and d) magnications.
Figs. 3 and 4 show TEM and AFM micrographs of CNC nanoparticles (as received). The average length (171 79.7 nm) and thickness (15.1 5 nm) of re-dispersed CNC nanoparticles were
determined from image analysis of TEM images containing over
150 particles. AFM images were used to estimate the 3D shape and
dimensions (length, width, and height) of CNC nanoparticles. A
Fig. 9. SEM image of CNCSFD6 (left) and its interior structure (right) at low (a and c) and high (b and d) magnications.
294
Fig. 10. Polarized light microscopy image of CNCSFD2 (left) and CNCSFD6 (right).
Fig. 11. BET specic surface area on CNC dried with different techniques.
295
Fig. 12. PLM images of a) CNCSD, b) CNCFD, c) CNCSFD2, d) PP, e) PPCNCFD-5, f) PPCNCSD2-5, and g) PPCNCSFD2-5.
Fig. 13. SEM images of a) pure PP, b) PPCNCSD-5, c) PPCNCFD-5, and d) PPNCSFD2-5.
296
Fig. 14. SEM images of PP melt inltration into CNCSFD2 agglomerates after 1 min of
mixing.
as regular or irregular cylindrical, cavities, cracks, and rugged areas connected to the surface of the material. In effect, in the BET technique, nitrogen gas is adsorbed on pore walls and starts to cover the pores. The
specic area is estimated based on the amount of adsorbed gas. This
could explain the low value of BET surface area (less than 1 m2/g) for
freeze and spray dried CNC, because nitrogen gas adsorption, if any,
can occur just on the external surface area of micron size particles,
shown in Figs. 5 and 6. Likewise, in CNCSFD0.5, nanoscale bers
(Fig. 7) can act as substrate for gas adsorption and a higher value of
BET surface area (20 m2/g) was obtained, due to more accessible area
for gas adsorption. Unlike CNCSFD0.5 particles, the word pore is
more meaningful for CNCSFD2 and CNCSFD6 particles, since there are
internal surfaces connected to external surface of the particles. It is not
logical to compare BET results of these structures with that in
CNCSFD0.5, in which there was no internal structure. CNCSFD2 had a
higher value of BET surface area (ca. 42 m2/g) than that of CNCSFD6
(ca. 35 m2/g). It could be due to the smaller pore size in CNCSFD2
which resulted in a higher BET surface area. It should be noted that
BET can detect micropores (less than 2 nm) and mesopores (between
2 and 500 nm). Hence, macropores (higher than 500 nm) should not
be considered in this technique. The space between lamellae (which is
in the micron size) in Figs. 8 and 9 can act as micro-channels for adsorption, which is not taken into account in the BET method.
Fig. 15. (top) Complex viscosity and (bottom) storage modulus versus angular frequency
for PP, PPCNCSD-5, PPCNCFD-5, and PPCNCSFD2-5.
297
Fig. 16. a) Tensile strength, b) tensile modulus and c) elongation at break for PP, PPCNCSD-5, and PPCNCSFD2-5.
5. Conclusion
Separation of CNC nanoparticles into individual nanoparticles is
quite challenging, particularly for CNC nanoparticles in parallel orientation, because the required separation force is higher than the C\C bond
force. Thus, polymer chain scission and degradation can take place before particle separation.
298