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Powder Technology 261 (2014) 288298

Contents lists available at ScienceDirect

Powder Technology
journal homepage: www.elsevier.com/locate/powtec

Effect of drying conditions on cellulose nanocrystal (CNC) agglomerate


porosity and dispersibility in polymer nanocomposites
V. Khoshkava, M.R. Kamal
Department of Chemical Engineering, McGill University, 3610 University Street, Montreal, Quebec H3A 2B2, Canada

a r t i c l e

i n f o

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.

is a drying process that occurs at low temperature by sublimation and


is suitable for thermosensitive materials. Spray freeze drying (SFD) is a
cryogenic atomization technique consisting of two main steps: (i) an
aqueous solution is atomized directly/indirectly into a cryogenic liquid,
such as liquid nitrogen, and (ii) freeze drying of the frozen suspension
below the triple point of water. This technique has been used in the ceramic, food and pharmaceutical industries [712]. However, to our
knowledge, it has not been used in conjunction with CNC.
Most attempts to prepare polymer/CNC nanocomposites via melt
mixing were not successful to disperse CNC and therefore enhance mechanical properties of polymer [1316]. Therefore, most polymer nanocomposite preparations with CNC have been limited to solution mixing
[1720]. One of the challenges in polymer nanocomposite eld is nanoparticle dispersion evaluation in polymer matrices. This becomes a severe challenge for CNC as an organic nanoparticle dispersed in an
organic medium such as polymer matrices. Thus, microscopy as a direct
and conventional tool for dispersion is limited for polymer/CNC nanocomposites. On the other side, rheology as a sensitive tool to nanoparticle dispersion could be employed as a complementary technique.
In this work, the effect of spray freeze drying on the microstructure
of CNC agglomerates is studied. The porous CNC micro-particles (agglomerates) obtained by SFD could be used in applications where porosity is of interest, such as polymer nanocomposites, drug delivery,
scaffolds, and catalysts. In a previous study [21], we found that thermodynamic analysis of energy requirements is not sufcient to achieve
good dispersion of CNC in polymer melts, because kinetics factors
should be also taken into consideration. Therefore, the relation between

V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

CNC agglomerate structure and its dispersibility in polymer matrices is


analyzed, with due consideration to particle strength and polymer diffusion standpoint. The morphological, rheological, and mechanical properties of polymer nanocomposites containing CNC agglomerates
prepared with different drying techniques (SD, FD, and SFD) are also
investigated.
2. Background
2.1. Dispersion of nanoparticles
Inter-nanoparticle forces and interaction energy play an important
role in the preparation of polymer nanocomposite systems. The magnitude of van der Waals interaction energy and forces between two isolated nanoparticles depends on the geometry of nanoparticles, as well as
inter-particle distance. CNC can be considered as a cylindrical nanoparticle with 7 nm radius and 150 nm length [21]. Table 1 shows equations
and estimates for inter-particle interaction energy and force between
two cross and parallel CNC cylindrical particles. Ui, Fi, AH, R, L, and z are
the van der Waal interaction energy between particles, inter-particle
force, Hamaker constant, particle radius, cylinder length, and interparticle distance, respectively. AH, the Hamaker constant, is dened
as [22]:
2

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

289

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

It is important to note that separation of two CNC nanoparticles with


parallel alignment by a pulling force is not achievable, because the
break-up force for C\C covalent bond is around 2.513.4 nN [25,26]. If
this amount of force is provided by employing a very strong mixing element/accessory, polymer chain scission can occur during pulling. As a
result, there is no guarantee that all agglomerated nanoparticles will
separate during mixing, and some of them remain intact. However,
not all CNC particles are in parallel orientation. Other alignments
(such as cross) need less hydrodynamic pulling force to be separated
(see Table 1).
2.2. Dispersion of micro-particles
The above discussion dealt with the separation (dispersion) of two
isolated nanoparticles. However, nanoparticles are usually in an aggregated or agglomerated structure. Dispersion or dispersive mixing of agglomerates in polymeric systems requires the reduction of the size of
the agglomerates. The nal size is determined by the competition

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

Fig. 1. (top) Pulling and (bottom) peeling mechanism of separating nanoparticles.

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V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

Fig. 2. Agglomerate strength a) versus particle radius and b) porosity.

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

where and are porosity and agglomerate radius, respectively.


Replacing inter-nanoparticle force (parallel alignment, Table 1) in
Eq. (3) yields:

1 AH R0:5 L
:
16a2 z2:5

Considering low and high viscosity systems with viscosities in the


range 110 k Pas, we found that the hydrodynamic stresses at a typical
mixing shear rate of 100 s1 would be in the range of 0.11 MN/m2.
Fig. 2a shows agglomerate strength versus particle radius according to
Eq. (4) for CNC nanoparticles at 190 C, where typical polymerller
mixing usually takes place. It shows that agglomerate strength increases
as agglomerate radius decreases. At the beginning of mixing process
when particle size is large, hydrodynamic forces are higher than cohesion forces. Thus, particle de-aggregation takes place via the breakup
mechanism [27,29,30]. In other words, at the beginning of the mixing
process, agglomerates are weak and they can be easily broken. However, particle strength becomes higher than hydrodynamic forces as particle size is reduced below a certain size. It has been suggested that the
erosion mechanism becomes the dominant mechanism of particle size
reduction at this point [27,30,31]. The erosion mechanism is very
slow, in comparison to the rapid breakup mechanism. Various approaches are used to facilitate breakup and erosion, such as increasing
residence time, using different types of mixing elements, rotor speed,
and feeding rate, in addition to using compatibilizer and masterbatch
preparation [3239].
Fig. 2b also shows agglomerate strength of CNC agglomerates versus
porosity for different CNC agglomerate sizes at 190 C, where typical
melt mixing usually takes place. CNC nanoparticle with 7 nm radius,
150 nm length and 18.6 mJ/m2 surface energy at 190 C has been considered [21]. It shows that the strength of agglomerate decreases

when porosity increases. Furthermore, polymer inltration is enhanced


as porosity of the particle increases [40]. Thus, agglomerate particle microstructure can play an important role in the facilitating dispersion.
3. Experimental
3.1. Materials
Polypropylene (PP) (Pro-fax SR549M, LyondellBasell, USA) with
0.9 g/cm3 room temperature density and 11 g/10 min MFI (2.16 kg
load, at 220 C) was used as matrix. Cellulose nanocrystal (CNC) white
powder was supplied by FPInnovations (FPI), Canada. CNC was prepared using the conventional spray drying method [6]. Henceforth, as
received refers to spray dried CNC.
3.2. Drying of CNC
For a typical experiment, 0.56.5 g of CNC powder was dispersed in
100 mL of distilled water, using a shear mixer (IKA, ultra-turrax T25,
Germany) at room temperature. The resultant CNC suspension was sonicated for 5 min in an ice bath with a tip sonicator (Qsonica Q700) at amplitude 2, in order to obtain individual CNC nanoparticles. For freeze
drying, CNC aqueous suspension was poured in a glass vessel and placed
in a refrigerator set at 50 C, overnight. Then, the frozen suspension

Fig. 3. TEM image of CNC nanoparticles (as received).

V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

291

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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V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

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.

3.4.2. Rheological measurements


All rheological measurements were made using a stress-controlled
rheometer (Physica MCR 500, Anton Paar, Graz, Austria) with parallel
plate geometry (plate diameter of 25 mm) at 190 C under nitrogen atmosphere. Disk-shape samples were positioned in the parallel plate xture and left for 10 min to minimize any residual stress resulting from
sample preparation. The gap was set at 1 mm by gradually squeezing
the sample. Rheological properties of these samples were determined
in small amplitude oscillatory shear (SAOS) mode. Both neat PP and
PP/CNC nanocomposites were found to be stable for a period of over
2 h. Hence, thermal degradation was assumed to be negligible during
the rheological measurements. The linear viscoelastic region was rst
determined using strain sweep from 0.01 to 1000% at a constant frequency of 1 rad/s. The linear viscoelastic region was determined by a
5% reduction in the elastic modulus, G, of the sample.

3.4.3. Mechanical properties


Mechanical testing of the nanocomposites was performed on
compression molded samples. Dumbbell-shaped specimens (gage
length width thickness = 15 5 0.5 mm3 ) were cut from
molded sheets using a Tensilekut I-series sample milling machine
(Maryville, TN, USA) for tensile testing according to ASTM D 882-9.
The tensile tests were conducted with an MTS Universal Tensile

Fig. 7. SEM image of CNCSFD0.5 (left) and CNCSFD1 (right) at low (a and c) and high (b and d) magnications.

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293

Fig. 8. SEM image of CNCSFD2 (left) and its interior structure (right) at low (a and c) and high (b and d) magnications.

Testing machine (Eden Prairie, MN, USA). A crosshead speed of


5 mm/min was used for all tests. The average values of 5 experiments are reported.

4. Results and discussion

3.4.4. BET surface area analysis


The specic surface area and porosity of CNC particles prepared by different drying techniques were measured from N2 adsorption/desorption
using a Micromeritics TriStar at 77 K and pressures down to 105 Torr.
Prior to the analysis, the adsorbed moisture on the ne powder surface
was eliminated by preheating the powders at 100 C for 4 h.

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

4.1. Spray dried CNC

Fig. 9. SEM image of CNCSFD6 (left) and its interior structure (right) at low (a and c) and high (b and d) magnications.

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V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

Fig. 10. Polarized light microscopy image of CNCSFD2 (left) and CNCSFD6 (right).

typical example of size analysis for three CNC nanoparticles is


presented in Fig. 4. The width or thickness (2833 nm), horizontal
distance between two cross points, and diameter (46 nm), corresponding maximum height between mica substrate and nanoparticle, of CNC nanoparticles are shown along the abscissa and
ordinate, respectively. The difference between CNC thickness values
obtained from TEM (ca. 15 nm) and AFM (ca. 30 nm) is due to the
size of AFM tip (ca. 10 nm) known as tip-convolution [41].
SEM and crossed light microscopy images of CNC particles (as received) are displayed in Fig. 5. The shape of CNC particles is not a
round sphere, due to shrinkage during the spray drying procedure. Similar agglomerate characteristics for spray dried CNC have been reported
[5,6]. A broad range of CNC particle sizes (ca. 530 m) is observed in
Fig. 5. The structural characteristics of spray dried CNC particles are controlled by four forces: capillary, van der Waals, hydrogen bonding, and
electrostatic repulsion forces. The rst three forces cause CNC nanoparticles to collide, while electrostatic repulsion caused by the negative
charge on CNC surface balances over aggregation. Therefore, fast aggregation cannot occur and nanoparticles have enough time to reach the
best orientation, for energy minimization before collision. In other
words, a random collision cannot take place, which results in a compact
and dense powder. The product of the spray drying technique is a powder consisting of compact particles due to capillary, van der Waals and
hydrogen forces attracting nanoparticles during drying. The powder
particle size becomes smaller than the initial drop size due to evaporation and the capillary effect involved in spray drying technique. The diffusion of a hydrophobic polymer melt into packed spray dried CNC

Fig. 11. BET specic surface area on CNC dried with different techniques.

particles (agglomerates) is very difcult. Thus, it allows relatively


small contact area between the polymer and CNC. This would require
large hydrodynamic forces to cause breakdown of particles to a size or
structure that would allow larger surface contact.
4.2. Freeze dried CNC
Fig. 6 displays SEM and PLM images of CNC aqueous suspension
(3 wt.%) which was rst frozen in a refrigerator at 50 C and then
freeze dried. Large (N100 m) ake/sheet structure of CNC was formed
by slow cooling (in the refrigerator). Unlike the spray drying technique,
ice crystal growth is the main reason of CNC aggregation in the freeze
drying technique. Indeed, ice crystal nucleation and growth take place
throughout the bulk of the sample, and water crystallization occurs
slowly. Therefore, CNC nanoparticles are pushed away from the ice crystal region. As a result, CNC nanoparticles collide and agglomerate. As in
the case of the spray drying technique, freeze drying of aqueous suspensions produced dense particles.
4.3. Spray freeze dried CNC (CNCSFD)
Fig. 7 shows SEM images of spray freeze dried CNC from aqueous
suspension at two different concentrations: 0.5 and 1 wt.%. Henceforth,
they are referred to as CNCSFD0.5 and CNCSFD1, respectively. As illustrated, at low concentrations (ca. b 2 wt.%), a porous agglomerated
CNCs in a lament-like structure,(consisting of interconnected nanobers) of CNC was created (Fig. 7ab) Hereafter in this manuscript referred to as lament-like agglomerates. In this concentration regime,
there was no structural integrity due to the low number density of
CNC nanoparticles inside the drops. In other words, there were not
enough nanoparticles to preserve the spherical shape of drops after
the atomizer. Fibers in CNCSFD0.5 were connected and have a high aspect ratio (if applicable), in comparison with CNC individual nanoparticles (Figs. 3 and 4). The bers in CNCSFD0.5 had thickness in the range
of ca. 1030 nm (minimum and maximum). The length cannot be readily estimated as the bers were connected, but it appears to be in micron
scale. Similar structure was observed in CNCSFD1 particles (Fig. 7cd).
The thickness of bers was in the range of ca. 2065 nm range (minimum and maximum). It is higher than that in CNCSFD0.5, due to a
higher CNC number density in CNCSFD1. Thus, there are more chances
for CNC aggregation before or during freezing. The driving force for
nanoparticle assembly is not capillary forces anymore. Similar to freeze
drying, the main driving force for CNC aggregation is ice crystal growth
(solidication) which causes the dispersed phase to collide and agglomerate. The size of crystals and the growth rate depend on the cooling
rate. However, in comparison with freeze drying, much less aggregation
is expected to occur due to high rapid cooling rate.
More aggregation is expected at a higher CNC concentration during
SFD, due to higher collisions and aggregation. Unlike CNCSFD0.5 and

V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

295

Fig. 12. PLM images of a) CNCSD, b) CNCFD, c) CNCSFD2, d) PP, e) PPCNCFD-5, f) PPCNCSD2-5, and g) PPCNCSFD2-5.

CNCSFD1, spherical foam-structure particles were formed in the case of


spray freeze dried CNC from aqueous suspension at concentrations 2
(CNCSFD2) and 6 wt.% (CNCSFD6), as depicted in Figs. 8 and 9. Unlike
spray dried CNC, there was no sign of shrinkage, and particles have a
spherical appearance. Pores were left by sublimation of ice crystal during freeze drying. It is important to point out that the word pore is applicable for CNCSFD2 and CNCSFD6 particles, contrary to CNCSFD0.5
and CNCSFD1. Pore structure, shape and size seemed to be inuenced
by CNC concentration. Pore sizes were less than 350 nm in the case of
CNCSFD2 (Fig. 8ab), and some particles were broken up either during
spraying or sample preparation for SEM characterization. A typical example is shown in Fig. 8cd. The particle had probably been split. The interior structure indicates that the particle is made of lamellae/sheets
which originate from the center and contain pores with less than 350
nm pore size.
Lamella/sheets consist of almost 100% crystal unit structure (i.e. CNC).
At high concentration (6 wt.%), pores were larger (Fig. 9ab). The SEM

image of a broken CNCSFD6 particle is shown in Fig. 9cd. Lamella/


sheet structure can be seen in this particle, too. However, the internal
structure seems somewhat different from CNCSFD2 in which sheets
looked wavier. Fig. 10 displays crossed polarized light microscopy of
CNCSFD2 and CNCSFD6 particles. Like polymer spherulites, a distinct
Maltese cross pattern is observed, indicating an ordered internal structure. It is noteworthy that spray dried CNC particles appeared as yellow
spherical objects without a birefringent property Fig. 5.
The BET technique allows the estimation of pore size and surface
area by measuring the specic amount of adsorption/desorption of nitrogen gas. As mentioned earlier, depending on CNC concentration in
the SFD method, different structures were formed. The interpretation
and comparison of BET data of these structures are difcult. Fig. 11
shows BET results for spray dried CNC (as received), freeze dried CNC,
CNCSFD0.5, CNCSFD2, and CNCSFD6. For CNCSFD0.5 and CNCSFD1
with a lament-like agglomerate structure (see Fig. 7 denition of
pore geometry is quite challenging. Pores usually have geometry such

Fig. 13. SEM images of a) pure PP, b) PPCNCSD-5, c) PPCNCFD-5, and d) PPNCSFD2-5.

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4.4. PP/CNC nanocomposite


4.4.1. Morphological studies by microscopy
Fig. 12ac shows PLM results of spray dried (as received), freeze
dried and spray freeze dried CNC, respectively. Fig. 12df shows PLM
images of unlled PP (Fig. 12d), PPCNCSD-5 (Fig. 12e), PPCNCFD-5
Fig. 12f, and PPCNCSFD25 (Fig. 12g), respectively. In light of the observations in Fig. 12ac, it can be concluded that platelet and shiny yellow
objects in Fig. 12ef are spray dried and freeze dried CNC agglomerates,
correspondingly. It seems that CNC agglomerate size remains almost intact (the same as origin size) with no size reduction as a result of melt
mixing with the PP matrix. The PLM result for PPCNCSFD25 is shown
in Fig. 12g at the same processing conditions. Unlike Fig. 12e and
Fig. 12f, there is no trace of large particle at this scale of observation.
This explains that it is much easier to de-agglomerate or disperse the
highly porous spray freeze dried CNC agglomerates than that of the
compact agglomerates obtained by conventional spray drying or freeze
drying techniques.
Fig. 13 shows SEM images of neat PP, PP containing 5 wt.% spray
dried (PPCNCSD-5) and freeze dried CNC (PPCNCFD-5). The presence
of CNC agglomerates in Fig. 13b (spherical shape spray dried CNC) and
Fig. 13c (lamella/sheet like freeze dried CNC) is an indication of unsuccessful de-aggregation of the conventional drying methods (spray and
freeze drying) of CNC suspensions. There is no sign of signicant polymer inltration in spray and freeze dried agglomerates, since they are
compact and dense. For instance, NCCSD appeared as a different color
(whitish) than the polymer matrix (grayish) in SEM images indicating
the absence of signicant polymer melt inltration. On the other hand,

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.

V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

297

Fig. 16. a) Tensile strength, b) tensile modulus and c) elongation at break for PP, PPCNCSD-5, and PPCNCSFD2-5.

in PP containing 5 wt.% of CNCSFD2 (PPCNCSFD2-5), there was no trace


of CNCSFD2 agglomerates in PP, signifying the high efciency of deaggregation of spray freeze dried CNC, Fig. 13d. Fig. 14 shows SEM
image of PP containing CNCSFD2 at 2 minute mixing time. Polymer
melt inltration into the porous structure of CNCSFD2 agglomerates
can be seen in Fig. 14. In other words, PP melt inltration time is short
and occurs at the beginning of mixing. Then, CNC agglomerates are dispersed and distributed in the PP melt to reach the morphology seen in
Fig. 13d. The morphological results conrm the hypothesis of improved
dispersion of porous CNC microstructure discussed in the Background
section.
4.4.2. Rheological properties
The results of complex viscosity and storage modulus versus angular
frequency are shown in Fig. 15. PP showed a Newtonian behavior at low
frequencies. Adding 5 wt.% of spray dried CNC and freeze dried CNC into
PP melt did not change complex viscosity and it was almost
superimposed with PP curve. On the other hand, complex viscosity
was increased considerably followed by a shear thinning behavior
by addition of CNCSFD2 agglomerates into PP melt. Fig. 15 also
presents results of storage modulus of SAOS tests. Similarly, there
was no difference between storage moduli of PP, PPCNCFD-5, and
PPCNCSD-5. However, low frequency storage modulus was signicantly
increased by addition of 5 wt.% CNCSFD2 in PP (PCNCSFD2-5). The slope
of storage modulus decreased signicantly and a plateau at low
frequencies was obtained for PP sample containing 5 wt.% CNCSFD2.
The rheological behavior of PPCNCSFD2-5 is similar to other polymer
nanocomposites containing well dispersed anisotropy nanoparticles
exhibiting a signicant low frequency viscosity upturn and a plateau
in storage modulus [42,43]. This is attributed to the presence of a network formation of nanoparticles within polymer matrix.

4.4.3. Tensile properties


Tensile properties were measured to determine the impact of CNC
microstructure on the tensile strength, elongation at break and modulus
of the PP/CNC nanocomposites. Fig. 16 shows the results for the tensile
strength, tensile modulus and elongation at break. There was not any
difference between tensile modulus of neat PP and PPCNCSD-5. The
PPCNCSFD2-5 samples showed an increase in strength of greater than
20% compared to the pure PP or the PPCNCSD-5. The modulus of samples incorporating PCNCSFD1-5 43% higher than the modulus of PP.
Adding spray dried CNC agglomerates directly to the PP did not show
any enhancement of the PP modulus. Since a higher stiffness is desirable
in many applications, the increase in modulus due to incorporation of
spray freeze dried CNC agglomerates is promising and can be advantageous. As expected, the elongation at break is lowered with the addition
of the reinforcement. Addition of large amount of nanoller could reduce the viscous response or plastic deformability of a polymer matrix,
while enhancing the elastic response. Consequently it induces brittleness character to the polymer matrix. Moreover, the presence of inevitable agglomerate solid particulates could intensify the brittleness due
to stress concentration. The sample that was reinforced with spray
dried CNC did not show a large decrease. However, samples containing
CNCSFD2 had a very low elongation at break, as expected.

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

V. Khoshkava, M.R. Kamal / Powder Technology 261 (2014) 288298

CNC microstructure depends highly on employed drying techniques.


Spray and freeze drying yield a dense structure. The former produces
smaller particles with spherical shape, while larger particles with ake
structure are produced by the latter. On the other hand, spray freeze
drying is a better technique to control structure of CNC particles in the
resulting powder. The shape and internal structure of CNCSFD particles
depend on CNC aqueous concentration prior to spray freeze drying. In
the low concentration regime (b 2 wt.%) a lament-like agglomerate
morphology, including interconnected nano-scale bers, is obtained.
At higher concentrations, foam-like spherical particles are formed.
Agglomerate strength and polymer melt inltration time are both
reduced as porosity increases. According to this study, spray freeze
dried CNC has higher potential for realizing a good degree of dispersion
within polymer matrices in the production of nanocomposites and
other nano-structured products. Experimental results conrm better
dispersion of spray freeze dried CNC in PP than those prepared by
spray and freeze dried techniques. Low frequency complex viscosity
and storage modulus of PP were signicantly increased by addition of
CNCSFD. Moreover, adding CNCSFD with lament-like agglomerate
structure increased 20% tensile strength and 43% tensile modulus of PP.
Acknowledgment
The authors would like to acknowledge nancial support from the
Natural Sciences and Engineering Research Council of Canada (NSERC),
McGill University, and NIPMMP Strategic Network and FPInnovations
for supplying the CNC for this project. The authors would like to thank
Ms. Mohini Ramkaran for AFM images from the Center for SelfAssembled Chemical Structures and the Facility for Electron Microscopy
Research (FEMR) at McGill University for the use of AFM and electron microscopy facilities. The authors would also like to thank Dr. P. Woodadams
for the rheometry facility.
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