International Journal of Biological Macromolecules 85 (2016) 370–378

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International Journal of Biological Macromolecules

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

Exploring the effect of cellulose nanowhiskers isolated from oil palm

biomass on polylactic acid properties
M.K. Mohamad Haafiz a,∗ , Azman Hassan b,∗∗ , H.P.S. Abdul Khalil a , M.R. Nurul Fazita a ,
Md. Saiful Islam c , I.M. Inuwa b , M.M Marliana b , M. Hazwan Hussin d
a
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
b
Faculty of Chemical and Energy Engineering Universiti Teknologi, Malaysia
c
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400, UPM Serdang, Selangor, Malaysia
d
Lignocellulosic Research Group, School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia

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

Article history: In this work, polylactic acid (PLA) reinforced cellulose nanowhiskers (CNW) were prepared through
Received 5 November 2015 solution casting technique. The CNW was first isolated from oil palm empty fruit bunch microcrys-
Received in revised form talline cellulose (OPEFB-MCC) by using 64% H2 SO4 and was designated as CNW-S. The optical microscopy
17 December 2015
revealed that the large particle of OPEFB-MCC has been broken down by the hydrolysis treatment. The
Accepted 1 January 2016
atomic force microscopy confirmed that the CNW-S obtained is in nanoscale dimension and appeared in
Available online 6 January 2016
individual rod-like character. The produced CNW-S was then incorporated with PLA at 1, 3, and 5 parts
per hundred (phr) resins for the PLA-CNW-S nanocomposite production. The synthesized nanocompos-
Keywords:
Cellulose nanowhiskers
ites were then characterized by a mean of tensile properties and thermal stability. Interestingly to note
Microcrystalline cellulose that incorporating of 3 phr/CNW-S in PLA improved the tensile strength by 61%. Also, CNW-S loading
Polylactic acid showed a positive impact on the Young’s modulus of PLA. The elongation at break (Eb ) of nanocompos-
Tensile properties ites, however, decreased with the addition of CNW-S. Field emission scanning electron microscopy and
Thermal analysis transmission electron microscopy revealed that the CNW-S dispersed well in PLA at lower filler loading
before it started to agglomerate at higher CNW-S loading (5 phr). The DSC analysis of the nanocomposites
obtained showed that Tg, Tcc and Tm values of PLA were improved with CNW-S loading. The TGA anal-
ysis however, revealed that incopreated CNW-S in PLA effect the thermal stability (T10, T50 and Tmax ) of
nanocomposite, where it decrease linearly with CNW-S loading.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction an alternative to micro-sized reinforcements in composite mate-

Recently, plethora studies have been done on the different
approch in production and isolation of cellulose nanoparticle [1–5].
The use of this nanoparticles as a reinforcement phase in the com-
posite production has attracted huge interest among researchers
[1–7]. The principal reasons for the utilization of cellulosic materi-
als are its high specific strength and modulus compared to other
engineering materials, and its reinforcing potential [8]. Due to
their availability, ease of chemical and mechanical modification as
well as their biocompatibility, renewability and a high axis ratio
(L/d), cellulose nanoparticles have attracted enormous attention as
∗ Corresponding author at: Division of Bioresources, Paper and Coating, School
of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia.
Fax: +60 4 657 3678.
∗∗ Corresponding author.
E-mail addresses: mhaafiz@usm.my, mohamadhaafiz@gmail.com
(M.K.M. Haafiz), azman@cheme.utm.my (A. Hassan).
rials [1,9]. It is well known that native cellulose can be readily
hydrolyzed to micro or nanocrystalline. Hydrolysis of lignocel-
luloses has been reported to result in micro or nanocrystalline
cellulose [1]. It was reported that these nanocrystalline cellulose or
cellulose nanowhisker (CNW) are usually ∼100–300 nm in length
and ∼3–10 nm in width [10,11]. The term whiskers are used to des-
ignate elongated crystalline rod-like nanoparticles, whereas the
designation nanofibrils should be used to designate long flexible
nanoparticles consisting of alternating crystalline and amorphous
strings [3].
The use of CNW as reinforcement material will lead to a fully
degradable and renewable biodegradable nanocomposite [12].
CNW have been obtained after the removal of the amorphous
region that result in the formation of high-purity single crystals.
This material has a mechanical strength equivalent to the bind-
ing forces of adjacent atoms [3]. The resultant highly ordered
structure produces not only unusually high strength but also
significant changes in electrical, optical, magnetic, dielectric,

http://dx.doi.org/10.1016/j.ijbiomac.2016.01.004
0141-8130/© 2016 Elsevier B.V. All rights reserved.
 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378
Fig. 1. Optical micrograph images for (a) before hydrolysis (b) after hydrolysis.
conductive, and even superconductive properties. The tensile
strength properties of whiskers allow the processing of the highest
attainable composite strengths and high-volume content reinforce-
ments [13,14].
A disadvantage of CNW is that the crystallites have to be iso-
lated, and incorporation of the crystallites in a matrix usually
involves problems in controlling the dispersion level [13,14]. How-
ever, according to Pandey et al. exposure to mechanical dispersion
or ultrasonication would permit the dispersion of CNW aggregates
and finally produce stable colloidal suspensions [15]. In addition
proper treatment of MCC with sulfuric acid (H2 SO4 ) will not only
generate isolated cellulose whiskers but also a negatively charged
surface resulting from the esterification of hydroxyl groups by sul-
phate ions formed a stable colloid system [16]. These nanomaterials
which show unique properties when incorporated in different poly-
mers have been sourced from kraft pulp, sugar beet pulp, wheat
straw, bacterial cellulose, and hemp fiber [17].
Malaysia is currently acclaimed as the largest producer and
exporter of palm oil in the world. Earlier studies by Basiron [18],
showed that the Palm Oil industry in Malaysia generates more
than 18 million tonnes of palm oil annually, thus becoming a
major economic pillar for the country. Consequently, enormous
amounts of lignocelluloses residues from oil palm industry such
as oil palm empty fruit bunches (OPEFB) were generated by the
palm oil industry [19]. OPEFB, a non-woody fibrous residue, which
remains after the liquid oil has been extracted, has not received
much commercial utilization. This biomass is readily available at
minimal cost. The development of a technique that can process
these bio-residuals into high-value added product (i.e., CNW) is of
Fig. 2. The AFM images for (a) OPEFB-MCC and (b) CNW-S.
371
great interest. Therefore this study focused on the isolation of CNW
from oil palm empty fruit bunches microcrystalline (OPEFB-MCC)
by acid hydrolysis technique and designated as CNW-S. The nano-
sized cellulose particle obtained was then used as reinforcement
phase in the polylactid acid (PLA) matrices for the development
of green nanocomposites (PLA-CNW-S). PLA is biopolymers which
can be derive from the fermentation of corn. It has good mechan-
ical and biodegradable properties. However, due to low thermal
stability, slow degradation rate, and medium gas barrier properties
limited the use of this biopolymer [16]. Therefore incorporating
PLA with the renewable reinforcement filler like CNW-S could be
of great interest in order to enhance some of PLA limitation while
maintaining their transparency and biodegradability properties.
2. Materials and methods
2.1. Material
Polylactic acid (Nature WorkTM PLA 3001D) in pellet form was
obtained from NatureWork® LLC, Minnetonka, MN USA. It has
a specific gravity 1.24 g/cm3 and melt flow index (MFI) around
15 g/10 min (190 ◦ C/2.16 kg). All chemicals were used as received
and were secured from Merck, Malaysia.
2.2. Preparation of PLA and PLA-CNW-S nanocomposites
A CNW-S was produced from OPEFB-MCC and used as rein-
forcement filler. The production of OPEFB-MCC and CNW-S were
described in detail in author’s early publication [6,20]. A 10 wt%
372 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378

Fig. 3. FESEM micrograph of fracture cross-section for (a) PLA, (b) PLA-CNW-S 3, (c) PLA-CNW-S 3 (detail view), (d) PLA-CNW-S 5 and (e) PLA-CNW-S 5 (detail view).

solution of PLA pellets in chloroform was prepared by stirring the
solution in the water bath at 60 ◦ C for 2 h until the pellets were
fully dissolved [21,22]. The PLA solution was immediately cast on
the clean glass plates and left for the solvent to evaporate at ambi-
ent temperature for 48 h. The films obtained from the cast solution
were approximately 100 ␮m and noted as pure PLA. To prepare
the PLA-CNW-S nanocomposite, 10 wt% solution of PLA was mixed
with different amounts of CNW-S (1, 3 and 5 phr) and the mixture
was kept at 60 ◦ C with strong agitation until the PLA pellets were
fully dissolved.
The nano filler used in this stage was in suspension form. There-
fore solvent exchange was done through centrifugation by using
Universal 32 Hettich (Newport Pagnell, England). In this stage
water was exchanged with acetone and acetone was exchanged
with chloroform. The filler was then sonicated in a Branson 2510
bransonic bath for 5 min to make sure the CNW-S is dispersed
homogenously inside the chloroform. The dispersed CNW-S was
then transferred into PLA with strong agitation approximately
2 h. The dissolved PLA containing CNW-S was then sonicated for
another 5 min. The solution was then casted on a clean glass plate.
The nanocomposite with approximately 100 ␮m in thickness was
obtained by solvent evaporation at surrounding temperature for
48 h before analysis. The PLA nanocomposites were designated as
PLA-CNW-S 1, PLA-CNW-S 3 and PLA-CNW-S 5.
3. Characterization
3.1. Optical microscopy
In this study, an optical microscope (OM) Leica DM 3000 was
used to observe microscopic changes on MCC, after hydrolysis
treatment. One drop of diluted (0.1 mg/100 ml) suspension was
dropped on the glass slide and observed with 10× magnified objec-
tive lens.
 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378
Fig. 4. TEM micrograph for (a) PLA, (b) PLA-CNW-S 3 and (c) PLA-CNW-S 5.
3.2. Microscopy analysis
Atomic force microscopy (AFM) measurements were performed
using SPA-300HV atomic force microscope with an SPI 3800 con-
troller. A dilute drop of CNW-S suspension (0.1 mg/100 ml) was
dispersed on the mica surface and allowed to dry at room temper-
ature prior to analysis. For the nanocomposites, the samples were
observed by using a field emission scanning electron microscopy
(FESEM) and transmission electron microscopy (TEM). FESEM was
conducted using a FESEM-EDX Oxford INCA 400 model at an accel-
eration voltage of 10 kV. The samples were sputter-coated with gold
to avoid charging. For TEM observation, the TEM model LEO LIBRA
was used; specimens with the thickness about 60 nm were pre-
pared using Leica Ultracut ultramicrotome with diamond knife. The
samples were examined at an accelerating voltage of 120 kV. The
TEM images were obtained by using soft imagine system software.
3.3. Tensile test
Mechanical test was done using the Instron 4400 Universal
Tester to measure the tensile strength at the point of breakage
for each sample. Tensile tests were carried out at room temper-
ature, according to the ASTM D882 type V. A fixed crosshead rate
of 12.5 mm/min was utilized in all cases and the results were taken
as an average of five tests [22].
3.4. Differential scanning calorimetry
Differential scanning calorimetry analysis was done by using
a PerkinElmer Pyris 7 Thermal Analyzer under nitrogen purge.
373
The sample was heated at 5 ◦ C/min in nitrogen flux from room
temperature to 250 ◦ C. Approximately 10 mg of nanocomposites
samples were transferred into hermetic aluminum pan and sealed.
The sample was then placed in the analyzer with an empty her-
metic aluminum pan as reference. The data of sample was recorded
continuously over the temperature and time intervals.
3.5. Thermogravimetric analysis
Thermogravimetric analyzer (TGA) Model 2050, (TA Instru-
ments, New Castle, DE) was used to characterize the thermal
stability of PLA and PLA-CNW-S. The specimens were scanned from
30 ◦ C to 600 ◦ C at the rate of 10 ◦ C/min and analysis was performed
under a nitrogen gas flow [22].
4. Results and discussion
4.1. Optical microscopy
Fig. 1 shows an optical micrograph of the OPEFB-MCC before
and after acid hydrolysis treatment. From the figure it can be seen
clearly that OPEFB-MCC (Fig. 1a) displayed large particles due to a
strong tendency of agglomeration [20]. It is however noteworthy
that after hydrolysis treatment the large aggregates had been bro-
ken down, whereby no particles could be observed (Fig. 1b). This
indicates that they might be in the nanosize particles. The optical
microscope resolution however is inadequate technique to observe
or detect the dimension and physical characteristic of CNW-S parti-
cles [13]. Therefore to confirm the separation of individual whiskers
after the hydrolysis treatment diluted suspension of CNW-S was
374 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378

Fig. 5. Effect of CNW-S loading on PLA nanocomposites (a) tensile strength, (b) elongation at break, and (c) Young’s modulus.

Fig. 6. The DSC curve for PLA and PLA-CNW-S nanocomposites.

 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378 375

Fig. 7. TGA and DTG curves for PLA and PLA-CNW-S nanocomposites.

observed using atomic force microscopy as discussed in detail in rod-like CNW-S from OPEFB-MCC with good aspect ratio (L/d) was
next section. successfully produced after the treatment. Hence, this will provide
the better reinforcement effect when CNW-S is incorporated with
PLA, which are discussed in the mechanical properties section.
4.2. Atomic force microscopy

The atomic force microscopy (AFM) images of OPEFB-MCC are
shown in Fig. 2a.The figure shows that OPEFB-MCC had regular
spherical particles. It is interesting to note that, after the hydrolysis
treatment, the morphological change on OPEFB-MCC was observed
as shown in Fig. 2b. The AFM analysis confirms that the individual
4.3. Field emission scanning electron microscopy
Since the mechanical properties of composites or nanocom-
posite are leaning on the polymer/filler interaction [23], the field
emission scanning electron microscopy (FESEM) was carried out to
376 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378

elucidate the interaction formed between CNW-S and PLA. FESEM Table 1
Glass transaction temperature (Tg ), cold crystalline temperature (Tcc ) and melting
images of fractured surfaces of PLA, and P-CNW-S nanocomposites
temperature (Tm ) for PLA and PLA-CNW-S nanocomposites.
are shown in Fig. 3. Fig. 3a shows a glossy and ordered morphology
of PLA fractured surface as also reported by Haafiz et al. [21,22]. On Formulation Tg (◦ C) Tcc (◦ C) Tm1 (◦ C) Tm2 (◦ C)
the other hand, the P-CNW-S displays homogeneous surface struc- PLA 48.1 104.1 146.90 150.05
ture, which suggested that CNW-S were uniformly distributed in P-CNW-S 1 48.9 103.34 148.10 151.03
the PLA. The good dispersion of CNW-S could be due to the strong P-CNW-S 3 49.1 101.1 147.10 151.22
P-CNW-S 5 49.47 95.64 146.11 151.60
interaction between CNW-S and PLA. Besides that, higher degree of
crystalline of CNW-S as reported earlier could be the reason for a
better dispersion of CNW-S in PLA [6]. This result is in good agree- the load bearing entity becomes efficient which then improved the
ment with previous observations reported by Garcia and Lagaron tensile strength [26]. For the specimens with more than 3 phr by
[24]. and Roohani et al. [25]. the tensile strength of PLA-CNW-S nanocomposite is dropped by
Fig. 3c and e shows the detail view of P-CNW-S fractured surface 22%. This drop in tensile strength is attributed to the agglomera-
at 3 and 5 phr. From the figures there is no clear evidence pertain- tion of CNW-S in PLA (Figs. 3 e and 4 c). This aggregation could act
ing to the present of the individual CNW-S in the PLA. This could as stress-centralized point and reduced the surface area interac-
be attributed to the nano size dimensions of CNW-S. It however, tion between CNW-S and PLA which leads to decrease the tensile
can be suggested that the white dot that appeared on the frac- strength of PLA-CNW-S 5 nanocomposites.
ture surface of PLA-CNW-S were assumed to be the perpendicular On the other hand, elongations at break (Eb ) of nanocompos-
plane of the CNW-S inside PLA. Wang et al. as well as Roohani et al. ites decrease dramatically with the additional of CNW-S in PLA
observed the similar outcomes when CNW used as reinforcement matrix as shown in Fig. 5b. The Eb decreased gradually as the CNW-
in poly(vinyl alcohol) and in soy protein thermoplastic respectively S concentration increased which rendered PLA more brittle. This
[17,25]. However, at 5 phr loading the aggregation of CNW-S in PLA observation may be attributed to the stiffening action of the CNW-S
is readily available (Fig. 3d). The fracture surface shows a relatively by restricting the segmental chain movement of PLA during ten-
rough structure suggesting that the interfacial adhesion between sile testing. Similar result was reported by Bulota et al. [29] when
PLA and filler is rather low [26]. This could be the reason, why they studied the mechanical behavior of PLA reinforced TEMPO-
the tensile strength and elongation at break (Eb ) of PLA-CNW-S Oxidized cellulose. Beside that the Eb is also affected by the volume
decreased gradually as discussed later in the mechanical properties fraction of the added reinforcement, the dispersion and interac-
section. tion between the reinforcement and the matrix as reported by Pei
et al. [30]. when cellulose nanocrystal from cotton cellulose used
4.4. Transmission electron microscopy as bio-based nucleation agents in poly(l-lactide) (PLLA).
The Young’s modulus of PLA-CNW-S nanocomposites increased
The enhancement in mechanical properties of composites and with the addition of CNW-S as shown in Fig. 5c. This revealed that
nanocomposite are depending on the absence of void, intact posi- the additions of CNW-S give the positive impact to the PLA-CNW-
tion of filler, interfacial bonding between filler and the absence of S nanocomposites. According to Cheng et al. [31] the increase in
filler agglomerations [26,27]. In order to get a better understanding Young’s modulus with increasing filler loading can be explained
in the changes on mechanical performance of PLA with additional by increased in stiffening effect from the filler which is a typical
of CNW-S, transmission electron microscope (TEM) was used. TEM characteristics filler/polymer composite. Beside that the high crys-
images of PLA and PLA-CNW-S at 3 and 5 phr loading are shown tallinity index of filler also is the reason for increasing of Young’s
in Fig. 4(a–c). It can be clearly seen in Fig. 4a that the microtome modulus [22,23,28].
section of PLA displays a smooth and clean surface feature. Mean-
while, Fig. 4b reveals that at 3 phr CNW-S loading, the filler are able 4.6. Differential scanning calorimetric analysis
to disperse homogenously inside the PLA matrices. The good dis-
persion of CNW-S in PLA could be the main factor in tensile strength The differential scanning calorimetric (DSC) was carried out to
improvement. However, at the highest filler loading (5 phr) the observe the effect on thermal properties of PLA after incorporated
aggregated of CNW-S occurred as displayed in Fig. 4c. This phe- with CNW-S. In order to minimize the influences of any residual
nomenon is similar to the observation by Liu et al. [28] could be the moisture presented, thermal history as well as other side effect
reason for reduction in mechanical properties of PLA-CNW-S 5. such as solvent traces in the samples, the DSC data presented are
taken from the second heating cycle [32]. DSC thermogram of PLA
4.5. Mechanical properties and PLA-CNW-S are shown in Fig. 6 and the resultant data of glass
transition temperature (Tg ), cold crystalline temperature (Tcc ) and
4.5.1. Tensile strength melting temperature (Tm ) are summarized in Table 1. Fig. 6 indi-
The effects of CNW-S loading on the tensile properties of pure cates the Tg , Tcc and Tm of the PLA-CNW-S nanocomposites. The
PLA and PLA-CNW-S nanocomposites are shown in Fig. 5(a–c). The Tg of PLA-CNW-S is slightly higher than that of the PLA (Table 1).
incorporation of microcrystalline cellulose from oil palm empty This indicates that the addition of CNW-S lead to the reduction in
fruit bunches (OPEFB-MCC) into the PLA matrices did not show PLA chain flexibility as Tg value is mainly related to the flexibility
any improvements in both tensile strength and elongation at break of polymeric segments. This observation is in a good agreement
(Eb ) of the composites as compared to pure PLA [21]. However, the
addition of CNW-S from OPEFB-MCC in PLA matrix indicated a dif- Table 2
ferent behavior in tensile strength properties. It is clear from Fig. 5a Thermal properties of PLA and PLA-CNW-S nanocomposites.
that the tensile strength of the nanocomposites was improved with
Formulation Degradation temperature (◦ C)
the increasing in CNW-S loading up to 3 phr before decrease with
higher CNW-S loading. This enhancement has been attributed to Ton T10 T50 Tmax
the good dispersion and stiffness between the filler and polymer PLA 295.93 331.99 359.57 363.62
matrix. Consequently, filler-matrix interaction becomes more pro- PLA-CNW-SO4 1 294.61 325.01 349.90 354.02
nounced and better interfacial adhesion was formed between the PLA-CNW-SO4 3 291.50 322.24 348.17 353.37
PLA-CNW-SO4 5 290.13 318.11 346.08 349.63
CNW-S and PLA. Therefore the stress transfers to the filler, which
 M.K.M. Haafiz et al. / International Journal of Biological Macromolecules 85 (2016) 370–378
with the results reported Baheti et al. [26], and Bulota et al. [29],
in which they were using jute nanofiber and tempo-oxidized cellu-
lose from birch pulp respectively as reinforcement in PLA. Besides
that this phenomenon could be related to the hydrogen bonding
interaction between OH group from PLA and CNW-S that induced a
restricted mobility of polymer chain. Therefore the decrease in the
chain mobility associated with Tg will increase the energy required
for Tg to occur [28]. On the other hand the Tcc values of PLA-CNW-
S are shifted to lower temperature as compared to the PLA. The
low Tcc observed during heating is indicated by faster crystalliza-
tion induced by CNW-S which acts as nucleating agent for PLA.
Therefore decreased the free energy barrier and fastens the crys-
tallization [26,28,33].
From Fig. 6, it is noteworthy that the melting peak of PLA and
PLA-CNW-S showed double melting peak (Tm1 and Tm2 ). In this
study the highest temperature endotherms were taken as the Tm .
According to Baheti et al. the highest temperature (Tm2 ) is a perfect
crystalline structure of PLA rather than lower temperature (Tm1 ).
From the observation the Tm value of PLA was enhanced with the
addition of CNW-S [26]. The improvement in Tm value with addi-
tion of CNW-S could be due to nucleating ability of CNW-S to
develop more heterogeneous crystalline morphology in PLA, con-
sequences increase the Tm value. Similar conclusion was arrived
from Baheti et al. [26], when wet mild jute nanofiber was used as
reinforcement in PLA, and by Frone et al. [33] in characterized the
thermal properties of PLA reinforced cellulose nanofiber obtained
from commercial available MCC.
4.7. Thermogravimetric analysis
In order to investigate the thermal performance of the PLA and
PLA-CNW-S nanocomposites, thermogravimetric analysis (TGA)
and derivative thermograms analysis (DTG) were performed. As
reported earlier by Haafiz et al. [22], incorporated PLA with CNW
obtained from OPEFB-MCC by swelling treatment improved the
thermal properties of PLA nanocomposites. On contrary as can be
seen from Fig. 7 and Table 2, the thermal stability of PLA-CNW-S
nanocomposites shows different behavior where, the thermal per-
formance of nanocomposites is slightly lower as compared to the
pure PLA.
The decreasing in thermal stability of PLA-CNW-S nanocompos-
ites is readily apparent as the CNW-S loading increased (1–5 phr).
The result was in agreement with earlier reported by Bras et al. [10].
During incorporated baggase cellulose whiskers as reinforcement
in natural rubber nanocomposites. Beside that the lower decompo-
sition temperature for PLA-CNW-S could be due the lowest onset,
T10 , T50 , and Tmax temperature of CNW-S as reported earlier by
the present author’s [6]. On the other hand the used of H2 SO4 in
isolation of cellulose nanowhiskers probably cause the catalytic
dehydration due to the present of sulfate group on the PLA surface
which decreased the thermal stability of PLA-CNW-S [10]. However
according to Wang et al [17]. This phenomenon could be over-
come by neutralized the acid sulphate group in CNW-S with NaOH.
When CNW-S was neutralized or H2 SO4 group was eliminated the
degradation temperature of CNW-S will probably shifted to higher
temperature, consequently will improve the thermal stability of
PLA-CNW-S nanocomposite.
5. Conclusion
Cellulose nanowhiskers (CNW-S) have been successfully iso-
lated from OPEFB. Atomic force microscopy revealed that the
CNW-S obtained had rod-like shape particles, with estimated
aspect ratio (L/d) more than 30. The TEM and FESEM indicated
that at 3 phr CNW-S loading, the fillers are homogeneously dis-
377
persed in the PLA matrices before the agglomeration took place at
5 phr CNW-S loading. The tensile strength of the nanocomposites
increased with addition of CNW-S up to 3 phr before decreasing at
further fillers loading due to the agglomeration. The Young’s mod-
ulus of the obtained nanocomposite showed the positive impact
to the filler loading. The elongation at break of PLA-CNW-S how-
ever, decreased linearly with the CNW-S loading due to polymer
chain movement restriction. It interesting to note that, Tg, Tcc and
Tm of PLA-CNW-S improved with the CNW-S loading as revealed
by DCS analysis. The TGA and DTG of the nanocomposite however,
slightly decrease as compared to the PLA when the CNW-S loading
increase. The fabricated PLA-CNW-S nanocomposite had shown the
potential to be used in coatings, membranes, and food agro based
packaging as well as in the automotive applications where the high
thermal stability is not a main requirement.
Acknowledgment
Short Term Research Grant 304/PTEKIND/ 6313194 and Funda-
mental Research Grant Scheme (FRGS) 203.PTEKIND.6711500.
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