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Nanocrystalline cellulose (NCC): A renewable nano-material for polyvinyl

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Article  in  European Polymer Journal · September 2012

DOI: 10.1016/j.eurpolymj.2012.08.008

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 European Polymer Journal 48 (2012) 1829–1837

Contents lists available at SciVerse ScienceDirect

European Polymer Journal

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

Macromolecular Nanotechnology

Nanocrystalline cellulose (NCC): A renewable nano-material

for polyvinyl acetate (PVA) adhesive
Alireza Kaboorani a, Bernard Riedl a,⇑, Pierre Blanchet a,b, Marco Fellin c, Omid Hosseinaei d,
Sequin Wang d
a
Département des sciences du bois et de la forêt, Faculté de foresterie, de géographie et de géomatique, Université Laval, 2425, rue de la Terrasse, Québec, QC,
Canada G1V 0A6
b
Nanotechnologies for Wood Products, FPInnovations, 319 rue Franquet, Québec, QC, Canada G1P 4R4
c
CNR IVALSA, Consiglio Nazionale delle Ricerche – Istituto per la Valorizzazione del Legno e delle Specie Arboree I – via Biasi 75 – 38010 S. Michele all’Adige
(TN), Italy

MACROMOLECULAR NANOTECHNOLOGY
d
Center for Renewable Carbon, University of Tennessee, 2506 Jacob Drive, Knoxville, TN 37996-4570, USA

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

Article history: In this study nanocrystalline cellulose (NCC) was used to improve the performance of
Received 2 May 2012 polyvinyl acetate (PVA) as a wood adhesive. NCC was added to PVA at different loadings
Received in revised form 3 August 2012 (1%, 2% and 3%) and the blends were used as binder for wood. Block shear tests were done
Accepted 13 August 2012
to evaluate bonding strength of PVA at different conditions; dry and wet conditions, at the
Available online 19 August 2012
elevated temperature (100 °C). The mechanical properties of PVA film and its composites
with NCC were measured by nanoindentation technique. Thermal stability and structure
Keywords:
of nanocomposites were studied by thermogravimetric analysis and atomic force micros-
Durable wood adhesives
Polyvinyl acetate (PVA)
copy (AFM). The block shear tests demonstrate that NCC can improve bonding strength
Nanocrystalline cellulose (NCC) of PVA in all conditions. Hardness, modulus of elasticity (MOE) and creep of PVA film were
Wood joints also changed positively by the addition of NCC. Thermal stability of PVA was significantly
Nanoindentation improved as NCC was added to PVA. Structural studies revealed that variations in shear
strength and other properties can be related to the quality of NCC dispersion in the PVA
matrix.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction resistance, durability, isolation and also not having carbon

Recently there has been a strong tendency to use so
called ‘‘green materials’’ for the industry. The tendency
has forced the industry to look for renewable materials
with the least impact on the environment. One of the indus-
tries that can benefit from this trend and subsequently
experience significant and constant growth is wood indus-
try. Wood can provide the market with the prospects which
cannot be offered by the other materials. Wood has a great
potential to become the dominating material for the con-
struction. As a material for the construction, wood has un-
ique properties; such as high strength, flexibility, fire
⇑ Corresponding author.
E-mail address: Bernard.Riedl@sbf.ulaval.ca (B. Riedl).
finger print. Introduction and development of engineered
wood products (EWPs), which can be produced in different
shapes and sizes, has opened new markets for wood indus-
try and expand the current markets.
Adhesives play an important role on the performance of
EWPs. Production of EWPs with high performance needs
durable adhesives. Commercial durable wood adhesives
contain formaldehyde, causing concerns on the health dur-
ing the production and the service of EWPs. Wood industry
is under increasing pressure to eliminate formaldehyde
from its products. Hence, wood industry is looking for
alternatives. Polyvinyl acetate (PVA) is a good alternative
to replace some wood adhesives containing formaldehyde.
PVA is a linear and thermoplastic polymer. It is water-
soluble, biodegradable with the excellent chemical

0014-3057/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.eurpolymj.2012.08.008
 1830 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837
resistance and has no toxic action on the human body. As a
wood adhesive, utilization of PVA is very simple and its
curing does not need high temperatures. The main draw-
back of PVA is its weak performance towards humid condi-
tions and elevated temperatures. These drawbacks limit
the usage of PVA in the applications where high perfor-
mance is required in humid conditions and at elevated
temperatures. So far two approaches have been used to in-
crease the performance of PVA: (1) Copolymerizing vinyl
acetate with more hydrophobic monomers or functional
monomers [1–3], and (2) blending PVA with other adhe-
sives or hardeners [4–13]. These strategies can increase
some properties of PVA at the expense of reducing some
other properties. Moreover, some additives are so acidic
that they can damage wood subtracts, finally affecting
the overall performance of wood joints. For instance,
copolymers of vinyl acetate and butyl acrylate or ethylene
can increase water resistance and toughness of the adhe-
sive, but will reduce its tensile modulus and stiffness, espe-
cially at elevated temperatures [12].
The introduction of nanotechnology has opened new
MACROMOLECULAR NANOTECHNOLOGY
opportunities for the industries to develop a new genera-
tion of composites with high performance. Past research
has showed that nano-clay and nano-aluminum oxide par-
ticles can be used to boost the performance of wood adhe-
sives [14,15]. There has been always concerns on the
health risks posed by nano-clay and nano oxide metal par-
ticles, however. Also the renewability of these kinds of
nano-particles has been always under question. Such con-
cerns gave a momentum to introduction of renewable and
more eco-friendly nano-materials. Cellulose is the most
abundant organic polymer in the biosphere and the main
constituent of wood. Cellulose has a nano-structure which
can be employed in nanotechnology.
Cellulose fibrils consist of different hierarchical micro-
structures commonly known as nano-sized microfibrils.
These nano-sized fibrils are again made-up of a combined
crystalline and amorphous parts and this crystalline region
is named in the literature nanocellulose or nanowhisker
[16]. Nanocrystalline cellulose (NCC) is obtained by the
acid hydrolysis of cellulose under conditions where the
amorphous regions are selectively hydrolyzed. For wood-
based NCCs, the remaining crystalline regions are 3–
10 nm in diameter and 100–300 nm long and retain the
natural cellulose I crystalline structure [17,18].Among
their interesting characteristics, NCCs are abundant and
renewable. They exhibit also a low density as compared
to mineral fillers (around 1.5 g cm3) and a high form fac-
tor of about 70 together with a high specific area of
150 m2 g1. They have been shown to lead to remarkable
reinforcing properties in such different matrixes as sty-
rene–acrylate latex [19], starch [20], polyhydroxybutyrate
octanoate [21] or poly(ethylene oxide) [22]. In most cases,
the reinforcing effects came from the percolating network
of NCC together with good interfacial compatibility be-
tween the matrix and the fillers.
The hypothesis of this study is that using NCCs as rein-
forcing nano-materials improves the performance of PVA
as a wood adhesive. Such improvement can expand the
applications of PVA, especially in the wood construction
domain in which durable materials with high performance
are required. The main objective of this research is to de-
velop durable eco-friendly wood adhesives with an appli-
cation in construction field. The effects of adding NCCs on
the mechanical properties, morphology and thermal stabil-
ity of PVA will be discussed in this paper.
2. Materials and methods
2.1. Materials
A commercial grade of polyvinyl acetate (PVA) was re-
ceived in liquid form. Nanocrystalline cellulose (NCC), pro-
vided kindly by Forest Products Laboratory in Madison, WI.
USA was used as reinforcing material, (in 5.5% suspension).
Black spruce (Picea mariana Mill.), which were obtained
from trees grown in province of Québec, Canada was used
as wood substrates.
2.2. Preparation of nanocellulose/PVA composites
A certain amount of the suspension of NCC was added
to PVA, depending on the percentage of nanocellulose in
PVA. The blends of PVA with nano-cellulose were mixed
for 30 min. For TGA, nanoindentation and AFM, samples
of nanocomposites were prepared by casting the NCC–
PVA composites on Teflon sheets. Prior to further analyses,
the sheets of nanocomposites were allowed to dry at room
temperature for at least two weeks.
2.3. Fabrication and tests of wood joints
Blends of PVA and NCC were used to bond wood joints.
Black spruce was used as substrates. Prior to gluing, the
moisture content of wood was fixed at 12% by conditioning
wood to 20 °C and 60% relative humidity for four months.
After applying glue on the surface of wood, the samples
were pressed in an MTS hydraulic test machine with
50 kN capacity at 2.46 kg/cm2 pressure for three hours. Be-
fore testing, glued samples were conditioned to 20 °C and
60% relative humidity for two weeks. 20 samples were
tested for each set of formulation.
Shear strength of wood joints was measured in dry
and wet states, and at an elevated temperature. An MTS
hydraulic test machine with 50 kN capacity was used for
load application and the data was acquired by a computer.
Wood failure and maximum load were recorded for each
test. The block shear tests were carried out according to
ASTM D905-98. The sizes of samples for ‘‘wet state’’ tests
were the same as those for dry state tests. For ‘‘wet state’’
tests, the samples were taken directly out of the water
after being immersed in water for 24 h. Before the tests,
excess water was wiped off from the samples. During the
water immersion period, temperature of water was main-
tained at 23 ± 1 °C.
Block shear tests at the elevated temperature were car-
ried out according to ASTM 7247-07. Samples made of
black spruce were heated in an oven, having a temperature
controller with an integral and derivative (PID) control
algorithm, until the temperature of middle of samples
reached 100 °C. On average, it took 30 min to reach
 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837
100 °C in the middle of samples. After reaching 100 °C in
the middle of samples, the samples were kept at 100 °C
for 15 min more, followed by the immediate block shear
test. The shear strength of sample was measured by an
MTS hydraulic test machine.
2.4. Characterization of the nanocellulose/PVA composites
2.4.1. Nanoindentation
Oliver and Pharr in 1992 introduced a technique, nano-
indentation, to characterize the localized material proper-
ties [23]. Conventional measurements of mechanical
properties only give a value for each test. In return, nano-
indentation technique provides an opportunity to measure
the mechanical properties of composites materials in de-
sired areas. In this technique, the areas under test can be
selected, giving different values depending on the place
of tested areas. A typical nanoindentation profile for deter-
mination of localized mechanical properties in polymer
composites is shown in Fig. 1. In the technique, a perma-
nent plastic deformation is created in the surface of a
material being tested.
Hardness, elastic modulus (MOE) and creep of the
material can be calculated by using the load-displacement
data from the nanoindentation tests. For an indentation
depth (h), the hardness (H) of a sample can be calculated
from the following equation:
Pmax
H¼
A pure PVA and its composites with NCC were embedded
where Pmax is the load measured at a maximum depth of
penetration (h) in an indentation cycle, while A is to the
projected area of contact between the indenter and sample
at Pmax.
In theory, the elastic modulus should be size indepen-
dent [24], but analyzing polymers by NI causes a number
of complications summarized under the term indentation
size effect, which means that the elastic modulus tends
to increase with decreasing penetration depth of the in-
denter pyramid. Also viscoelastic creep during unloading
may affect the slope of the unloading curve, and thus the
Fig. 1. The loading profile of nanoindentation.
1831
calculated elastic modulus. Comparing elastic moduli (E)
of polymers from bulk measurements and indentation
tests, results often show that Ebulk < Esurface [25].
From the initial slope of the unloading curve the
unloading stiffness (S) is determined and the reduced elas-
tic modulus Er is calculated according to Eq. (2).
1 pffiffiffiffi S
Er ¼ p pffiffiffi ð2Þ
2 A
Er is termed the reduced elastic modulus because it
takes into account the compliance of the indenter tip
according to Eq. (2).
   
1 1  m2m 1  m2i
¼ þ ð3Þ
Er Em material Ei indenter
The elastic modulus Em of the specimen was calculated
according to Eq. (3) using Poisson’s ratios m determined in
a previous study [26]. Ei and mi stand for the elastic modu-
lus and the Poisson’s ratio of the indenter. Since the com-
pliance of diamond is very small compared with that of
the tested polymers, the term representing the indenter
MACROMOLECULAR NANOTECHNOLOGY
properties (subscript indenter) in Eq. (3) was disregarded.
h2  h1
C IT ¼  100 ð4Þ
h1
Indentation creep CIT (Eq. (4)) [27] was defined as the
relative change of the indentation depth while the applied
load remains constant (Fig. 1).
To prepare the samples for the nanoindentation test,
ð1Þ
in Spur epoxy resin. Spur epoxy resin is used as an embed-
ding medium for electron microscopy of biological sam-
ples. The curing was performed in a vacuum oven at
70 °C for 7 h. An ultramicrotome (Leica, Vienna, Austria)
was used to make a very smooth surface, by avoiding cre-
ating any default, on the surface of sample. A five-minute
epoxy adhesive was used to glue the resin-embedded sam-
ples to an acrylic block. The acrylic block was then
mounted onto an ultra-microtome. First a glass knife was
used to level surface of the samples and then further on,
creating a smooth surface was completed by a diamond
knife. All nanoindentation experiments were performed
on a Triboindenter (Hysitron, Minneapolis, MN) equipped
with a three-sided pyramid diamond Berkovich tip. Before
nanoindentation tests, samples were conditioned at 21 °C
and 60% relative humidity for at least 24 h. Indentation
was performed in a load-controlled mode using three seg-
ments. The loading time, holding time, unloading time and
maximum indentation force (Pmax) are 5 s, 60 s, and 5 s and
150 lN for all testing samples, respectively. The separation
distance between each nanoindentation point was
0.05 mm.
2.4.2. Thermal stability
The thermal stability of pure NCC, pure PVA and their
nanocomposites was studied using a thermogravimetric
analyzer, Mettler Toledo TGA/SDTA 851e, on 13–15 mg of
samples over a temperature range of 25–700 °C at a heat-
ing rate of 10 °C/min under a nitrogen flow rate of
50 mL/min. In order to avoid unwanted oxidation, thermal
 1832 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837

stability measurements were conducted with the samples 12 120

Stress Wood failure
placed in high quality nitrogen (99.5% nitrogen and 0.5%
oxygen content) atmosphere. 10 100

Shear stress [MPa]

Wood failure [%]

2.4.3. Transmission electron microscopy 8 80
High-resolution transmission electron microscopy
(TEM) was carried out with a JEOL 100 CX II microscope 6 60
at 100 kV. The samples for TEM observations were pre-
pared from a solution with 0.5% NCC. The samples were 4 40
prepared by casting a drop of diluted aqueous dispersion
onto a 200 mesh holey copper grid covered with a carbon 2 20
film. To improve the contrast, the cellulose nanofibers
were stained with a 1 wt.% solution of uranyl acetate for 0 0
30 s. The sample was then dipped into a droplet of distilled Pure PVA NCC 1% NCC 2% NCC 3%
water for 2 s to remove the excess uranyl acetate. It was Blend name
then allowed to dry at ambient temperature overnight.
Fig. 2. Shear strength and wood failure of joints bonded by PVA and its
composites with NCC in dry state.
2.4.4. Atomic force microscopy (AFM)
AFM observations were carried out using a NanoScope
V, an atomic force microscope (Veeco Instruments Inc.), fit-
strength of PVA glue line. Wood failure value increased
ted with a Hybrid XYZ scanner. Atomic force microscopy
from 59% for pure PVA to 84% for adhesive with 1% NCC
MACROMOLECULAR NANOTECHNOLOGY

measurements were done under ambient air conditions

and finally to 97% for adhesive with 3% NCC. Such an in-
in tapping mode. The sensitivity of the tip deviation and
crease shows that NCC made the glue line of PVA stronger
the scanner resolution was 0.3 nm. The resolution was
than wood, causing failure in the wood rather than in the
set to 250 lines by 256 pixels for all observations. Surface
glue line. The loading level of NCC affected the perfor-
roughness was calculated in 10 lm  10 lm scan areas,
mance of PVA. Wood failure percentage increased as more
using the classical mean surface roughness parameters Ra
NCC was added to PVA.
and Rq (RMS). The parameters were calculated by the
Sriupayo et al. [28], Kvien and Oksman [29], Zimmer-
Research Nanoscope 7.2 software:
mann et al. [30], Favier et al. [31], Gong et al. [32] , Dalmas
1X n
et al. [33,34], Mathew et al. [35] and Lee et al. [36] reported
Ra ¼ jZi  Zav ej ð5Þ
n i¼1 that nanocellulose positively affected the strength of the
polymers. Favier et al. [31] stated that the intermolecular
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P forces between nanocellulose and the PVA matrix may
ðZi  Zav eÞ2
Rq ¼ RMS ¼ ð6Þ contribute to enhancement of strength of the PVA compos-
n ite films. The intermolecular forces keep the inherent
where Ra is the mean roughness, the arithmetic average of strength of the fibrils intact and results in enhancement
the absolute values of the surface height deviations, and Rq of the mechanical strength of the films. Some reports have
is the root mean square of the height and in both equations attributed the strong reinforcing effect of the NCC to the
Zi is the current Z value, Zave is the average of the Z values formation of a networked structure above percolation
within the given area and n is the number of points within threshold resulting from hydrogen bonding [37,38].
the given area.

2.5. Statistical analyses 8 100

7 90
A one way analysis of variance model was used to study Stress Wood failure
the effects of NCC loading on shear strength of wood joints. 80
6
The GLM procedure of the SAS program was used and pair
Shear stress [MPa]

70
Wood failure [%]

wise comparisons were then made using protected Fisher 5

60
LSD (Least Significant Difference).
4 50

3. Results 3 40

30
3.1. Bonding strength 2
20
1
10
Fig. 2 shows shear stress at failure of wood joints
bonded by pure PVA and its composites with NCC. Adding 0 0
Pure PVA NCC 1% NCC 2% NCC 3%
NCC to PVA did increase the stress but not in a significant
Blend name
way. Although not being significant in terms of the stress
at failure, adding NCC to PVA significantly increased the Fig. 3. Shear strength and wood failure of joints bonded by PVA and its
wood failure, proving its positive effects on bonding composites with NCC in wet state.
 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837
The values of shear stress at failure of wood joints
after spending 24 h in water are shown in Fig. 3. Nanocel-
lulose affected significantly shear strength of wood joints
after spending 24 h in water. Adding only 1% NCC to PVA
increased the strength by 63%. Further increase in NCC
(from 1% to 2%) increased shear strength of wood joints
but on a much smaller scale. An increase in NCC loading
from 2% to 3% did not change the strength much. The
improvement on water resistance of PVA was so high that
some failure occurred in glue line instead of wood. As
more NCC was inserted in PVA, the percentage of wood
failure increased, reaching its maximum value at 3%
NCC level (21%).
Sriupayo et al. [28], Choi et al. [39], Wang et al. [40], Lu
et al. [41] and Dufresne et al. [42] reported a reduction in
water uptake and diffusion coefficient of the polymers as
nanocellulose added to the polymers. The high crystallinity
of cellulose might be responsible for the decreased water
uptake at equilibrium and the decreased diffusion coeffi-
cient of the materials. The presence of NCCs in the polymer
can also create tortuosity in the nanocomposites films,
leading to slower diffusion processes and, hence, to a lower
permeability [43].
Fig. 4 shows the values of shear strength at 100 °C. NCC
affected PVA performance at the high temperature signifi-
cantly. Adding NCC to PVA doubled the shear strength of
PVA. There was no significant difference between different
loading levels of NCC. Adding only 1% NCC to PVA resulted
in a 100% increase in shear strength and further addition
did not change the strength much.
Angles et al. [20] and Favier et al. [31] reported that
incorporation of NCC in composites resulted in a significant
increase in mechanical properties, especially at tempera-
tures greater than the glass transition temperature. They
attributed the reinforcing effect to the formation of a rigid
NCCs network governed by the percolation threshold and
strong hydrogen bonding between NCCs. It was demon-
strated that the reinforcing effect of NCC lies in the forma-
tion of a rigid percolating filler network, due to hydrogen
bond interactions between NCCs [44–46].
4 100
Stress Wood failure
3
Shear stress [MPa]
2 50
1
0 0 0 0
0 0
Pure PVA NCC 1% NCC 2%
blend name
Fig. 4. Shear strength and wood failure of joints bonded by PVA and its
composites with NCC at the elevated temperature.
1833
3.2. Nanoindentation
Studying the response of composites materials to a
mechanical load in nano-scale helps to develop a better
understanding of impact of nano-materials on mechanical
properties of nanocomposites. Nanoindentation technique
can provide us with an opportunity to understand the re-
sponse of composites to a load in a nano-scale.
Values of hardness and their variations in pure PVA and
its composites with NCC are shown in Fig. 5. NCC addition
to adhesive increased average values of hardness signifi-
cantly. Adding only 1% NCC to PVA increased average value
of hardness by 70%. At 2% NCC loading, the extent of
improvement decreased and reached only 55%. An increase
in NCC loading form 2% to 3% resulted in a huge increase in
hardness (155%, more than double). Fluctuations in hard-
ness within the composites were also affected by NCC.
Variations in hardness were not very high in pure PVA.
As NCC was inserted into PVA, the variations in hardness
became high. The extent of variations in hardness was re-
lated to amount of the NCC in PVA. The higher the ratio of
MACROMOLECULAR NANOTECHNOLOGY
NCC to PVA, the greater the variation in hardness.
Average values of MOE and their variations for each for-
mulation measured by nanoindentation technique are
shown in Fig. 6. Average values of MOE were affected sig-
nificantly by addition of NCC. Adding 1% NCC to PVA in-
creased average value of MOE by 48% but adding more
NCC (2%) to PVA did not change MOE considerably. An in-
crease in NCC loading from 2% to 3% resulted in an impor-
tant increase in MOE. Film with 3% NCC showed the
highest value of MOE. The variations of MOE in different
parts of composites were influenced by adding NCC as
well. The values of MOE in pure PVA were pretty constant.
As NCC was added to the PVA matrix, the variations in MOE
became more important. The highest variations in MOE
were found in composites with 3% NCC.
One of drawbacks of PVA is its high creep. Nanoindenta-
tion technique provides an opportunity to measure creep
in different parts of film and analyze the effects of different
fillers on performance of the polymer. Creep measure-
ments conducted on the film of PVA and its composites
demonstrated that NCC has a significant effect on average
values of creep (Fig. 7). Adding NCC to PVA reduced the
creep. As the percentage of NCC in PVA increased, the effect
90 of NCC in reducing creep became more prominent. Adding
80
70
Wood failure [%]
60
40
30
20
10
NCC 3%
Fig. 5. Average values of harness for different PVA–NCC composites.
 1834 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837

Fig. 6. Average values of MOE for different PVA–NCC composites.

MACROMOLECULAR NANOTECHNOLOGY

Fig. 7. Average values of creep PVA and its composites with NCC.

3% NCC led to 55% reduction in creep. Variations of creep

were also affected by NCC. Pure PVA had a high variation
in creep throughout the matrix. In the formulations with Fig. 8. Mass loss (a) and its rate (b) for PVA and its composites.
NCC, the variations in creep were less. The smallest varia-
tions in creep were observed in the formulation with 3%
NCC. was similar to PVA composites in temperatures less than
The results of measuring hardness, MOE and creep by 235 °C. Between 235 and 340 °C, thermal stability of pure
nanoindentation technique demonstrate the great influ- NCC is less than its composites with PVA. Thermal stability
ence of NCC on the mechanical properties of PVA matrix. of pure NCC was better than its composites at tempera-
NCCs create an inhomogeneous matrix with different tures higher than 340 °C.
localized mechanical properties. Such a matrix shows im- To have a detailed view over mass loss pattern occurred
proved mechanical properties, capable of bearing higher during thermal stability tests, the dM/dT curves obtained
mechanical load as shown by bonding strength tests in this by derivation of mass loss/temperature data are given in
study. Fig. 8b. The dM/dT curves show the speed of mass loss dur-
ing thermal stability tests. Pure PVA has three peaks of
weight loss at 258, 331 and 436 °C. As a result of adding
3.3. Thermal stability NCC to PVA, one of the three peaks located at 258 °C disap-
peared. The second and biggest peak, located at 331 °C, re-
Mass loss of PVA and its composites (measured in the mained almost untouched but the third peaks located at
range of temperature) was used as a tool to evaluate the ef- 436 °C occurred at little bit higher temperatures. It has
fects of NCC on thermal stability of PVA. Thermal stability
of PVA was affected by NCC (Fig. 8). The direction of
changes in the thermal stability depended on the temper- Table 1
ature. At temperatures less than 340 °C, PVA with NCC had Values of ash contents and DTGmax for pure PVA, pure NCC and their
composites.
better thermal stability than pure PVA. In temperatures be-
tween 340 and 420 °C, PVA and its composites had almost Samples DTGmax (°C) Ash content (%)
the same thermal stability. At temperatures higher than Pure PVA 331.1 13.2
420 °C, NCC negatively affected the thermal stability of Pure NCC 305.6 15.8
PVA. No significant difference was detected between the PVA & 1% NCC 335.5 10.3
PVA & 2% NCC 337.0 8.9
nanocomposites having different amounts of NCC at tem-
PVA & 3% NCC 337.8 9.1
peratures less than 420 °C. Thermal stability of pure NCC
 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837 1835

decompose. For rod-like particles with an aspect ratio of

67, the percolation threshold is close to 1 vol.% [47]. The
formation of this cellulose network was supposed to result
from strong interactions between NCCs, such as hydrogen
bonds [48]. This mechanical percolation effect explains
both the reinforcing effect and the thermal stabilization
of the composite modulus for evaporated films.
Values of DTGmax degradation temperature and ash
contents for PVA and its composites are given in Table 1.
DTGmax degradation temperature is a temperature in
which the highest weight loss takes place (peak point in
dM/dT curve). Pure PVA has higher DTGmax than pure
NCC. Composites of NCC and PVA have higher DTGmax than
pure PVA and pure NCC. It means that NCC can change the
response of PVA towards temperatures. Ash content of PVA
was also affected by adding NCC. Composites with NCC
Fig. 9. TEM image of NCCs. have lower ash contents than pure PVA. NCC proportion
in PVA inversely affects the ash content of PVA.

been reported that the formation of a rigid network, result- 3.4. Transmission electron microscopy
ing from strong interactions between NCCs and the poly-

MACROMOLECULAR NANOTECHNOLOGY
mer (governed by a percolation mechanism) [19,31], Fig. 9 shows a TEM image of dilute suspension of NCCs.
induced a thermal stabilization on the composite up to The NCCs have a rod-like structure. Acrylic latexes have
227 °C, the temperature at which cellulose starts to been employed for a variety of applications including

Fig. 10. AFM amplitude mode analysis of PVA films with (a) 0%, (b) 1%, (c) 2 and (d) 3% NCC.
 1836 A. Kaboorani et al. / European Polymer Journal 48 (2012) 1829–1837
painting and adhesion. The suspension exhibited a colloi-
dal behavior. This is due to the presence of the positive
charges (NH3+) on the NCC surface, which resulted from
the protonation of the amino groups of chitin in acidic con-
ditions [49]. The suspension contains fragments consisting
of both individual microcrystals and aggregated microcrys-
tals. The rod-like NCCs were shown to have length values
of 150–250 nm and width on the order of 4–10 nm, leading
to an aspect ratio of 38–62.
3.5. Atomic force microscopy (AFM)
To further explore the fundamental interactions be-
tween NCC and PVA, composite of PVA containing different
loading of NCC (0%, 1%, 2% and 3%) were analyzed by atom-
ic force microscopy (AFM). The AFM images for the com-
posites are presented in Fig. 10. The images clearly
demonstrate a re-organization of the surface of the com-
posite films. Pure PVA film has a smooth surface as it has
low Ra and Rq (Table 2). Adding 1% NCC to the matrix did
not change Ra and Rq considerably, showing good disper-
MACROMOLECULAR NANOTECHNOLOGY
sion of NCC at 1% loading. Adding 2% and 3% NCC to the
matrix re-organized the surface as big jumps in Ra and Rq
were detected. Such high Ra and Rq are evidence for poor
quality of NCC dispersion in the matrix, and presence of
aggregates. Seemingly high interaction between PVA and
NCC (in the form of hydrogen bonding) prevented NCCs
to be dispersed uniformly in the matrix.
Comparing the results of morphological studies and
mechanical and thermal properties displays that thermal
stability and bonding strength (in wet conditions and at
the elevated temperature) have more sensitivity to the
quality of NCC dispersion in the PVA matrix. At 1% loading,
NCC improved the thermal stability and bonding strength
of PVA significantly. But adding more NCC (2% and 3%)
did not increase the properties beyond the extent obtained
by 1% addition. This trend is related to the quality of NCC
dispersion. At 1% NCC loading, significant improvement
on bonding strength and thermal stability was achieved
as quality of NCC dispersion was good. At 2% and 3% NCC
loadings, dispersion of NCC in PVA encountered difficulty,
as shown by the AFM results, and a poor dispersion of
NCC in the matrix was obtained leading to a leveling-off
of the improvement. In the context of the others studies
conducted on the reinforcement of PVA with inorganic
nano-materials [13,14], the extent of improvement
achievable by NCC is higher than that of inorganic nano-
materials, namely nano-clay and aluminum oxide. The
improvement is especially much higher for thermal stabil-
ity and bonding strength at wet conditions.
In this study unmodified and hydrophilic NCC was used
to reinforce PVA. Using such unmodified and hydrophilic
Table 2
Values of surface roughness for pure PVA and its composites with NCC.
Samples Rq (nm)
Pure PVA 39.9
PVA & 1% NCC 27.6
PVA & 2% NCC 140
PVA & 3% NCC 155
NCC led to agglomeration of NCC and difficulty in disper-
sion of NCC in PVA at high loadings (2% and 3%). The
agglomeration limits the extent of improvement that be
achieved by NCC. Modifying the surface of NCC a little bit
and imposing a slightly hydrophobic character on the sur-
face can help to prevent agglomeration of NCCs and to have
a better NCC dispersion in the matrix at a high loading. The
modification of surface should be done in controlled condi-
tions without making NCC too hydrophobic or degrading
its reinforcing effects.
4. Conclusions
NCC was found to be an effective nano-reinforcing
material for PVA. Bonding strength of wood joints was im-
proved significantly as NCC was inserted to PVA. The
improvement was measurable in terms of wood failure
percentage in dry condition and in terms of shear strength
in wet condition and at the elevated temperature. NCC in-
creased hardness and MOE of PVA film significantly. The
creep experienced a big reduction as NCC was added to
the PVA matrix (especially at high loadings of NCC). Ther-
mal stability of PVA gained big enhancement by the addi-
tion. The three levels of NCC loading affected thermal
stability in the same extent. Structural study of NCC–PVA
composites revealed that NCC changed the structure of
PVA. Fluctuations in properties of PVA as a wood adhesive
and a polymer at different loadings of NCC could be
explained by the quality of NCC dispersion in the matrix.
The thermal stability and bonding strength of wood joints
showed more sensibility to the quality of NCC dispersion in
the matrix.
Acknowledgements
The authors acknowledge financial support from Natu-
ral Sciences and Engineering Research Council of Canada.
The authors would like to express their thanks to Forest
Products Laboratory – USDA Forest Service for so kindly
providing nanocrystalline cellulose (NCC) for this research.
Thanks are also extended to FPInnovations for their
assistance.
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