Industrial Crops and Products 44 (2013) 192–199

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Industrial Crops and Products

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Fabrication of nanocelluloses from hemp fibers and their application for the
reinforcement of hemp fibers
Dasong Dai, Mizi Fan ∗ , Philip Collins
Civil Engineering Department, School of Engineering and Design, Brunel University, Kingston Lane, Uxbridge, Middlesex UB8 3PH, UK

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

Article history: A novel fabrication has been employed to produce nanocelluloses from natural fibers (hemp) and the
Received 12 September 2012 developed nanocellulose was then used as “coupling agent” to modify hemp fibers themselves.
Received in revised form 4 November 2012 The size distribution of nano-particles (nanocellulose) was measured by nanoparticle tracking analy-
Accepted 6 November 2012
sis (NTA). Results showed that the oxidation–sonication developed nanocellulose had wider size range
(29–281 nm) and the average size (100–112 nm). Morphologies of nanocellulose displayed a slight dif-
Keywords:
ference under field emission gun-scanning electron microscopy (FEG-SEM) and atomic force microscopy
Natural fibers
(AFM). Mechanical testing showed that the nanocellulose modification could improve the mechanical
Hemp fibers
Nanocellulose
properties of natural fibers significantly. The modulus, tensile stress and tensile strain of nanocellulose
Mechanical property modified hemp fibers were increased by 36.13%, 72.80% and 67.89%, respectively. FEG-SEM and X-ray
Interface property diffractogram (XRD) were used to reveal the mechanism of nanocellulose reinforcement on natural fibers.
FEG-SEM illustrated that the nanocellulose treatment had resulted in an effective distribution of nanocel-
lulose along the stria on the surface of fibers, giving rise to a significant increase in the tensile strength
of the treated hemp fibers. The XRD analysis also showed that the crystallinity index of the treated fibers
had increased from 55.17% to 76.39%. X-ray photoelectron spectroscopy (XPS) has been used to charac-
terize the surface of fibers and attenuated total reflectance-fourier transform infrared (ATR-FTIR) was
carried out to determine the surface chemical reaction in order to elucidate the interface properties and
self-modification mechanisms of the hemp fibers.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Natural fibers (hemp), which are rich in cellulose are abundantly
available and easy to handle and process. Due to low prices and the
steadily rising performance of technical and standard plastics, the
application of natural fibers came to a near-halt from 1940s (Bledzki
and Gassan, 1999; Mohanty et al., 2005). However, from 1990s, the
critical discussion about the preservation of natural resources and
recycling has led to a renewed interest concerning natural materials
with the focus on renewable raw materials. More recently, with an
increase in environmental awareness, exploiting natural fibers has
arose much interest and become of importance. To date, numerous
publications have reported about the applications of natural fibers,
e.g. pulp (Gutiérrez and del Río, 2005), ethanol (Kreuger et al., 2011)
and composite (Ramires et al., 2010).
The use of natural fibers to make low cost and eco-friendly com-
posite materials is a subject of great importance (Bismarck et al.,
2001). Compared with glass fiber-based composites, natural fiber-
based bio-composites display several excellent advantages, e.g. low
∗ Corresponding author.
E-mail address: mizi.fan@brunel.ac.uk (M. Fan).
density, renewable and low cost. However, these natural fibers dis-
play their drawbacks, e.g. higher polar and hydrophilic, which make
natural fibers both poorly compatible with polymer and result
in the loss of mechanical properties upon atmospheric moisture
adsorption (Belgacem and Gandini, 2005). Various treatments (e.g.
physical treatments (Ragoubi et al., 2010), chemical treatments (Liu
et al., 2007), biological treatments (Li et al., 2009)) on the nat-
ural fibers have been investigated by researchers to improve the
mechanical properties of fibers.
New technologies (e.g. nanotechnology, biological technology)
have also recently been employed by researchers to modify nat-
ural fibers and can be grouped into three approaches, namely, (1)
soaking; (2) layer-by-layer deposition; and (3) sonochemical depo-
sition. These approaches were mainly developed to immobilize
nanoparticles on the surface of natural fibers, which were used for
textiles in the finishing process. The nanotechnology-based finish
techniques give rise to new properties, e.g. anti-bacteria (Lee et al.,
2003; Tarimala et al., 2006; Ilić et al., 2009), self-cleaning (Qi et al.,
2007; Uddin et al., 2008; Veronovski et al., 2009), water repellent
(Yu et al., 2007; Tomšič et al., 2008; Bae et al., 2009) and UV light
blocking (Wang et al., 2005; Mondal and Hu, 2007; Becheri et al.,
2008) to the natural fibers and enhance the performance of final
clothing product (Pasta et al., 2010). The hemp fibers treated with

0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2012.11.010
 D. Dai et al. / Industrial Crops and Products 44 (2013) 192–199
Table 1
Experimental levels of NaOH and NaClO.
Experiment Addition of NaOH (%) Addition of NaClO (%)
Std 1 14 60
Std 2 10 70
Std 3 8 65
fungus Ophiostoma ulmi showed an improved acid–base charac-
teristics and resistance to moisture (Gulati and Sain, 2006); and
that the flexural strength and flexural modulus of the modified
hemp fibers–polyester composites were improved by 21% and 12%,
respectively. Bismarck et al. (Juntaro et al., 2007; Pommet et al.,
2008) used the bacteria Gluconacetobacter xylinus strain BPR 2001
to modify natural fibers (hemp fibers and sisal fibers). By using
biological technology, nanosized bacterial cellulose has been suc-
cessfully deposited around natural fibers, and such the adhesion of
fibers to renewable polymers improved.
The present work employed oxidation/ultrasonication to
fabricate nanocellulose from hemp fibers at first. Then, the nanocel-
lulose was used as “coupling agent” to treat hemp fibers. Size
distribution of nanocellulose was characterized by NTA, and mor-
phologies of nanocellulose were characterized by FEG-SEM and
AFM. Mechanical properties and interfacial properties of the mod-
ified natural fibers were investigated chiefly. FEG-SEM and XRD
were performed to reveal the mechanism of tensile strength
increase of the fibers with nanocellulose modification. XPS and
ATR-FTIR were carried out to investigate the surface properties
of natural fibers coated with unsaturated polyester with the aim
to reveal the mechanism of interface change and self-modification
mechanisms.
2. Materials and methods
2.1. Materials
Hemp yarns were obtained from Shanxi Greenland Textile Ltd.
Hemp fibers were supplied by a Hemp Farm & Fiber Company
Ltd., UK. Dodecyltrimethylammonium bromide (DTAB), ethyl-
ene diamine tetraacetic acid (EDTA), sodium hydroxide, sodium
hypochlorite and sodium sulfide were supplied by Sigma–Aldrich.
Unsaturated polyester was obtained from CFS.
2.2. Fabrication of nanocellulose
Hemp yarns were chopped into short fibers (length: 0.5–1 cm)
by scissors. Nanocellulose was prepared by the oxidation hydrolysis
of chopped short hemp fibers. The oxidation hydrolysis was carried
out at 65 ◦ C, 4 h under continuous agitation and sonication with
various sodium hydroxide and sodium hypochlorite, as shown in
Table 1. Yield of nanocellulose was worked out by the following
equation:
Wn
Yield % = × 100
Wf
where Wf is the weight of the shorted hemp yarns before hydrolysis
and Wn is the weight of nanocellulose after oxidation.
2.3. Modification of natural fibers
2.3.1. DTAB modification
Hemp fibers (1 g) were soaked in beaker (50 ml), which con-
tained 30 ml DTAB solution 0.05% (by the weight of dried fibers)
with pH value 11. The beaker was then loosely covered with a glass
and supported in an ultrasonic bath at 60 ◦ C for 1 h. After that, the
hemp fibers were washed with distilled water. Finally, the modified
193
hemp fibers were dried with vacuum oven at 70 ◦ C for 24 h and
conditioned at 20 ± 2 ◦ C and 65 ± 2% relative humidity before uses.
2.3.2. Nanocellulose modification
The DTAB modified hemp (0.5 g) fibers were soaked in beaker
(30 ml), which contained 2% nanocellulose suspension in room
temperature for 10 min. Then, the nanocellulose modified hemp
fibers were dried with vacuum oven at 70 ◦ C for 24 h and condi-
tioned at 20 ± 2 ◦ C and 65 ± 2% relative humidity before uses.
2.4. Tensile testing
The conditioned individual fiber was temporarily fixed on the
mounting card (Fig. 1) with adhesive tape. A droplet of glue was
applied on the center of both sides of the hole along the length
of card. Subject the test pieces to tensile strength test by using
Instron 5566 at a crosshead speed of 3 mm/min and with 25 mm
gauge length with screw grips (the capacity is 100 N with a resolu-
tion of 1 mN). About 20 samples were tested for untreatment, DTAB
treatment and nanocellulose treatment.
2.5. Resin adsorption measurements
Unsaturated polyester, which was ordered from CFS was diluted
with styrene until the volatile content was 95%. Hemp fibers (0.5 g)
with various treatments (without modification; DTAB modifica-
tion; nanocellulose modification) were, respectively, immersed in
20 ml of diluted unsaturated polyester in a glass bottle. 2% catalyst
(on the weight of unsaturated polyester) of catalyst was then added
into the bottle. After degassing the compounds with ultrasonic bath
for 5 min, the temperature was raised from room temperature to
80 ◦ C, and the compounds were treated for 15 min at 80 ◦ C. After
cooling, the fibers were washed with distilled water, and finally,
the fibers were dried with vacuum oven at 60 ◦ C for 24 h.
2.6. AFM
The AFM was used to examine the surface of nanocellulose. A
drop of the suspension was deposited onto freshly cleaved mica and
left to dry in a desiccating capsule with silica gel for a period of 12 h.
A Nanoscope IIIa microscope (Digital Instruments, Santabarbara,
CA, USA) with a multimode head was used for measurement. Sam-
ple was imaged in tapping mode. Height images were recorded. The
instrument was operated with a resonance frequency of 155 kHz,
1 Hz scan rate and a spring constant of 12–103 N m−1 .
2.7. ATR-FTIR
ATR-FTIR spectra were recorded on a PerkinElmer Spectrum one
Spectrometer. After resin adsorption experiment, the fibers with-
out and with nanocellulose treatment were mounted on an ATR
equipped with 3× bounce diamond crystal and an incident angle
of 45◦ was used. The instrument was operated under the following
(1) conditions: 4000–650 cm−1 range; 4 cm−1 resolution; 16 scans and
20 ◦ C.
2.8. FEG-SEM
About 50 ml nanocellulose suspension was dropped into petri
dish (diameter 55 mm). Then, the suspension was dried in vacuum
oven at 60 ◦ C. A thin nanocellulose film was obtained after dry-
ing. A small piece of the nanocellulose film was examined with
a Zeiss Supra 35 VP field emission scanning electron microscopy
(FEG-SEM). The test pieces were coated with thin layer platinum
on the surface in an Edwards S150B sputter coater to provide elec-
trical conductivity. Following coating, samples were observed and
194 D. Dai et al. / Industrial Crops and Products 44 (2013) 192–199
Fig. 1. Set-up of single fiber test: (a) specimen mount and (b) test specimen mounted on the mount (dimensions in mm).
operated at 10 kV using the secondary electron mode with images
collected digitally.
FEG-SEM images of hemp fibers without treatment and nanocel-
lulose treatment were also been taken. The test pieces were coated
with thin layer platinum according to the above protocol and then
observed under the same conditions as previously.
2.9. NTA
Nanoparticle tracking analysis (NTA) experiments were per-
formed using a digital microscope LM10 System (NanoSight,
Salisbury, UK). 1 ml of the diluted sample (concentration 0.001%)
was introduced into the chamber by a syringe. The particles of
nanocellulose in the sample were observed using the digital micro-
scope. The video images of the movement of particles under
Brownian motion were analyzed by the NTA, version 1.3 (B196)
image analysis software (NanoSight). Each video clip was captured
over 22 s. The detection threshold was fixed at 100, whereas the
maximum particle jump and minimum track length were both set
at 10 in the NTA software.
2.10. XPS
XPS was performed using a VG Escalab 210 system with an
aluminum anode (AlK␣ = 1486.6 eV) operating at 150 W with a
background pressure of 5 × 10−9 mbar. The low-resolution survey
scans were taken with a 1 eV step and 50 eV analyzer pass energy;
high-resolution spectra were taken with a 0.1 eV step and 50 eV
analyzer pass energy. The angle between X-ray beam and the sur-
face normal was kept at 0◦ and the depth of analysis was practically
10 nm. The atomic ratio of oxygen-to-carbon (O/C) was calculated
from their normalized peak areas as:
O IO SC
= ×
C IC SO
where IO and IC are the normalized integrated area of the peaks for
oxygen and carbon, respectively SC /SO is the corrected term for the
sensitivity factor.
2.11. XRD
Raw hemp fibers, DTAB modified hemp fibers and nanocel-
lulose modified hemp fibers were subjected to a powder X-ray
diffraction method analysis (PXRD) respectively. For this analysis,
a D8 advanced Bruker AXS diffractometer, Cu point focus source,
graphite monochromator and 2D-area detector GADDS system
were used. The diffracted intensity of CuK␣ radiation (wavelength
of 0.1542 nm) was recorded between 5◦ and 40◦ (2 angle range) at
40 kV and 40 mA. Samples were analyzed in transmission mode.
The crystallinity index (CI) was evaluated by using Segal et al.
(1959) empirical method as follow:
(I0 02 − Iam )
CI% = × 100 (3)
I0 0 2
where I0 0 2 is the maximum intensity of diffraction of the (0 0 2)
lattice peak at a 2 angle of between 21◦ and 23◦ , which repre-
sents both crystalline and amorphous materials. Iam is the intensity
of diffraction of the amorphous material, which is taken at a 2
angle between 18◦ and 20◦ where the intensity is at a minimum.
10 replicates were used.
3. Results and discussion
3.1. Size distribution and morphologies of nanocellulose
Fig. 2 presents the results of size distribution of nanocellu-
lose with various treatments. According the NTA, the size range
of nanocellulose for std 1, std 2 and std 3 is 31–281 nm, 38–278 nm
and 29–321 nm respectively, the average size of nanocellulose for
std 1, std 2 and std 3 is 100 nm, 112 nm and 103 nm, respectively.
Compared with acid hydrolysis (Morán et al., 2008), nanocellu-
lose fabricated by oxidation–sonication shows wider size range
(the acid hydrolysis gives 5–60 nm) and higher average size (the
acid hydrolysis gives 30.90 nm). However the NTA results disclose
(2) that oxidation–sonication also can fabricate nano-scale cellulose.
The yield of nanocellulose for std 1, std 2 and std 3 are 10.72%,
34.31% and 42.02%, respectively (Fig. 2). Std 3 was further char-
acterized by FEG-SEM (Fig. 3(a)) and AFM (Fig. 3(b)). According to
FEG-SEM characterization, the size of nanocellulose ranges from
45.45 nm to 168 nm. AFM image of nanocellulose shows a slight
difference with FEG-SEM, as shown in Fig. 3(b), not only par-
ticles can be observed in this image but also rod like of fibril
can be found. This may be due to the difference of preparation
of samples.
 D. Dai et al. / Industrial Crops and Products 44 (2013) 192–199 195

Fig. 2. Size distribution and picture from NTA video of nanocellulose (std 1, std 2 and std 3).

3.2. Mechanical properties of nanocellulose modified natural therefore we conjecture the increase of mechanical properties may
fibers be due to the “repair” of dislocation in the fibers.

3.2.1. Mechanical properties 3.2.2. FEG-SEM

Mechanical properties of hemp fibers with various treatments
were summarized in Table 2. It is apparent that both DTAB and
nanocellulose treatment enhance the mechanical properties of nat-
ural fibers, especially for nanocellulose treatment, compared with
raw fibers, the modulus, tensile stress and tensile strain of nanocel-
lulose modified hemp fibers increase by 36.13%, 72.80% and 67.89%,
respectively. As reported, dislocation is the weakest link in natu-
ral fibers (Ouajai et al., 2004; Eder et al., 2007; Dai and Fan, 2011),
The natural fibers before and after nanocellulose modification
were observed with FEG-SEM. As shown in Fig. 4(a), impurity and
interfibrillar gap can be found on the surface of raw hemp fibers.
Fig. 4(b) clearly shows the presence of nanocellulose around the
fibers. FEG-SEM micrograph shows that nanocellulose covers the
surface of the fibers with two ways, namely, (1) filling in the stria
and (2) bonding the inter-fibril on the surface of hemp fibers.
Compared with macro-fibers from nature, nanocellulose possesses

Fig. 3. Morphology of nanocellulose (a) by FEG-SEM (100,000×) and (b) by AFM (height image).
196 D. Dai et al. / Industrial Crops and Products 44 (2013) 192–199

Table 2
Mechanical properties of modified hemp fibers.

Experiment Diameter C.V. of Modulus C.V. of Tensile stress C.V. of Tensile strain C.V. of
(␮m) diameter (%) (GPa) modulus (%) at break (MPa) stress (%) at break (%) strain (%)

Unmodified 46.76 6.75 28.29 9.39 696.68 9.07 2.29 5.31

DTAB modification 45.10 9.65 29.83 7.95 735.29 7.65 2.47 9.98
Nanocellulose modification 51.39 7.05 38.51 8.44 1203.85 9.25 3.84 5.92

Fig. 4. FEG-SEM morphologies of untreated (a) and nanocellulose modified hemp fibers (magnification: (a) 20,000×; (b) 48,000×).

higher specific surface area (up to 170 m2 g−1 ) (Samir et al., 2004, Nanocellulose
CI Hemp fibers =55.17%
2005; Stenstad et al., 2008; Wagberg et al., 2008; Habibi et al., 2010), 5000 Modified Hemp fibers
CI DTAB modified =65.95%
it has a relatively high elastic modulus of 78–150 GPa as determined DTAB Modified
for a single nanocellulose fibril (Guhados et al., 2005; Cheng and Hemp fibers CI Nanocellulose modified =76.39%
4000
Wang, 2008; Iwamoto et al., 2009). Therefore, covering of nanocel- Hemp fibers
Intensity (a.u.)

lulose on the surface of fibers will introduce new properties onto I 002
fibers. The higher specific surface area will rough the fibers surface 3000
and may lead to a stronger interface with resin. The second advan-
tage of high specific surface area is based on the high density of 2000
hydroxyl groups (Stenstad et al., 2008), which will bond interfib- I004
ril through hydrogen bonding. Moreover, the attaching of higher
1000 I am
elastic modulus of nanocellulose may lead to a better mechani- I I101
101
cal performance for natural fibers. As described by Thygesen et al.
10 20 30 40
(2006), lamellae with 100 nm thick existed in S2 layer, delamina- 2
tion could be observed in this layer. Therefore, in the process of
modification, nanocellulose might penetrate into the lamellae in S2 Fig. 5. X-ray diffractogram of unmodified, DTAB and nanocellulose modified hemp
layer, these filling will give rise to increase the mechanical proper- fibers.
ties of S2 layer and might contribute to the dislocations reparation
of fibers. 3.3. Interface property of nanocellulose modified natural fibers

3.2.3. XRD Interfacial property of fibers is the main factor, which deter-
X-ray diffractogram was used to investigate the crystallinity mines the final performance of the fibers-based composites.
of unmodified, DTAB modified and nanocellulose modified hemp Various methods (e.g. micro-mechanical techniques (Mandell et al.,
fibers. An example of X-ray powder diffraction spectra from these
hemp fibers is given in Fig. 5. Crystallinity index analysis was
summarized in Table 3. It can be seen from Table 3 that the
Table 3
major crystalline peak of the hemp fibers with various treatments Intensity and crystallinity of modified hemp fibers.
occurs from 21.77◦ to 22.63◦ , which represents the cellulose crys-
tallographic plane (0 0 2, Bragg reflection). The minimum intensity Samples 2 (◦ ) Intensity Crystallinity
(a.u) index (%)
between 0 0 2 and 1 0 1 peaks (Iam ) is from 18.52◦ to 19.11◦ . The
crystallinity index for raw fibers, DTAB modification and nanocel- Iam I0 0 2 Iam I0 0 2
lulose modification is 55.17%, 65.95% and 76.39%, respectively. It Raw fibers 19.11 22.63 1822 4064 55.17
is apparent that after modification, crystallinity of hemp fibers DTAB modified fibers 18.52 21.77 1529 4491 65.95
increased significantly. This may be due to the removal of impurity Nanocellulose 18.58 21.94 1307 5538 76.39
modified fibers
on the fibers or attributed directly to attaching nanocellulose.
 D. Dai et al. / Industrial Crops and Products 44 (2013) 192–199 197

Table 4 8000 Atomic ratio of O/C

Absorbed resins of raw hemp fibers and modified fibers. 1 0.245 1 Unsaturated polyester
7000 2 0.272
Samples Absorbed resin (mg/0.5 g fibers) 3 0.356 2 DTAB-Nanocellulose fibers
6000 /Unsaturated polyester
Raw fibers 52.05 4 0.349

Intensity /cps
DTAB 33.65 5000
Nanocellulose modification 72.35 3 DTAB fibers/Unsaturated
4000 polyester

3000 4 Raw fibers/ Unsaturated

1980; Gaur and Miller, 1989; Yue et al., 1995), spectroscopic tech-
niques (Zadorecki and Rönnhult, 1986; Hua et al., 1987; Takase
and Shiraishi, 1989; Felix and Gatenholm, 1991), surface charac-
terization (Gassan et al., 2000; Montes-Morán et al., 2001; Park
et al., 2006)) have been developed for assessing interfacial property.
Especially, for spectroscopic techniques, researchers always use
Soxhlet extraction as pretreatment before FTIR or XPS characteriza-
tion (Park and Kim, 2000; Matuana et al., 2001). In the present work,
we develop a novel method without Soxhlet extraction pretreat-
ment for the measurement of polyester adsorption on the surface
of fibers and the characterization of fiber surface by FTIR and XPS.
The adsorbed unsaturated polyester on the surface of fibers with
various treatments was summarized in Table 4. Table 4 shows that
after nanocellulose treatment the resin adsorption was increased
from 52.05 mg/0.5 g fibers to 72.35 mg/0.5 g fibers, but for DTAB
treatment, the adsorbed resin was decreased from 52.05 mg/0.5 g
fibers to 33.65 mg/0.5 g fibers. This indicates that nanocellulose
modification can improve the interfacial properties of fibers. This
result is in agreement with those discussed in 3.2.2 in this present
paper. Namely, nanocellulose can increase the interface of fibers
with resins.
XPS is always used to study the chemical compositions of cellu-
losic and polymeric materials as well as their chemical interactions.
Fig. 6 shows XPS wide scans spectra for unsaturated polyester,
unsaturated polyester coated fibers, which were pretreated with
various methods. It can be seen that oxygen and carbon are the main
elements on the surface of fibers. High resolution of spectra at O1s
and C1s were shown in Fig. 7. Atomic ratio of O/C also is calculated
from this figure. Nanocellulose modification results in a decrease in
the O/C atomic ratio, which is 0.272 compared to O/C ratio for raw
fibers/unsaturated polyester or DTAB fibers/unsaturated polyester.
This value is similar with unsaturated polyester which is 0.245,
indicating that almost all of the surface of the fibers were covered
with the resin. For DTAB treatment and raw fibers, O/C atomic ratio
is 0.356 and 0.349, respectively. These results are in agreement
with the resin absorption measurement as illustrated above. The
results of XPS characterization indicates that the method that have
developed can be used as novel assessment way for the interface
property of fibers.
polyester
2000
1000 O1s C1s
0
535 530 292290288286284282280
Binding Energy /eV
Fig. 7. O1s and C1s narrow spectra of unsaturated polyester and fibers with untreat-
ment, DTAB and nanocellulose modification immersed with unsaturated polyester.
ATR-FTIR has been used extensively to investigate the surface
of fibers as well as the resin adhesion, and spectra subtraction is
useful in variety of situations, such as an inspection of incoming
raw materials, comparison of batches or samples, evaluation of
organic reactions, and so on. This present work employs spectra
subtraction to subtract unsaturated polyester spectrum from the
nanocellulose modified and un-modified hemps fibers which are
coated with unsaturated polyester, then compare these subtracting
spectra with raw unsaturated polyester. The differences spectrum
may be attributed to the effect of nanocellulose.
The ATR-FTIR spectra of pure unsaturated polyester (a), spec-
tra of polyester subtraction from nanocellulose modified fibers (b)
and raw fibers (c) after resin coating were presented in Fig. 8.
More details about regions 2 and 3 were shown in Fig. 9(a) and
(b). As can be seen, the subtracted spectrum b appears negative
absorbance in region 1 (from 3600 to 3345 cm−1 ). According to pre-
vious reports (Kondo, 1997; Singh et al., 2000), free hydroxyl groups
(C2 and C6) in cellulose were assigned around 3561–3358 cm−1 ;
moreover, nanocellulose possesses high density of hydroxyl groups
(Stenstad et al., 2008). The negative absorbance in spectrum (b) of
Fig. 8 may be due to the esterification between hydroxyl groups
at C2 and C6 of nanocellulose and carboxyl groups of unsaturated
polyester. This can be further proved from the peak at 1426 cm−1
(Fig. 9(a)) which is assigned with the H C H bending vibration
(Tarimala et al., 2006). Moreover, the appearance of peak around
1380 cm−1 can be clearly observed in spectrum a in Fig. 9(a) also
further support this observation. Generally, the peak at 912 cm−1
is assigned with C H (in CH CH) out-of-plane bending of styrene,
989 cm−1 is assigned with C H (in CH CH) out-of-plane bending

0.14
O1s C1s Region 3
284.5 eV a Pure unsaturated polyester
531.9 eV 0.12
b Unsaturatedpolyester from surface
of nanocellulose modified fibers a
0.10 c Unsaturatted polyesteer from surface
284.9 eV
Unsaturated polyester of raw fibers
Absorbance

532.1 eV 0.08

284.8 eV DTAB-Nanocellulose fibers b

0.06
/unsaturatedpolyeser
Region 2
531.5 eV 0.04
DTAB fibers/Unsaturated polyester Region 1
532.3 eV 3345 c
0.02
284.7 eV Raw fibers/Unsaturated polyester 3600
0.00
600 500 400 300 200 100 0 4000 3500 3000 2500 2000 1500 1000
-1
Binding Energy /eV Wavenumber /cm

Fig. 6. XPS wide scans spectra of unsaturated polyester and fibers with untreatment, Fig. 8. ATR-FTIR spectra of pure unsaturated polyester, subtraction from nanocel-
DTAB and nanocellulose modification immersed with unsaturated polyester. lulose modified fibers and raw fibers.
198 D. Dai et al. / Industrial Crops and Products 44 (2013) 192–199
a Pure unsaturated polyester
b Unsaturatedpolyester from
a surface of nanocellulose
surface of nanocellulose
modified fibers
c Unsaturatted polyesteer from 1380
surface of raw fibers
1374
b
1426
c c
1450 1400
-1
Wavenumber /cm
(a)
Fig. 9. ATR-FTIR spectra of pure unsaturated polyester, subtraction from nanocellulose modified fibers and raw fibers in 1475–1340 cm−1 (a) and 1300–650 cm−1 (b).
of unsaturated polyester (Rahmat and Day, 2003; Worzakowska,
2009), the disappearance of 912 cm−1 in spectrum indicates that
less styrene was absorbed on the surface of raw fibers. However this
peak appears in spectrum b in Fig. 9(b), showing that nanocellulose
modification can increase the adhesion of styrene on the surface
of modified fibers. The appearance of peak at 975 cm−1 in spec-
trum b and peak at 984 cm−1 in spectrum c show that unsaturated
polyester is adsorbed by both of the fibers.
4. Conclusions
Oxidation–sonication has been successfully employed to pro-
duce nanocellulose directly from natural fibers (hemp fibers), with
NTA, FEG-SEM or AFM characterizations showing consistent out-
comes. The developed nanocellulose has then successfully been
used as “coupling agent” to modify hemp fibers with novel modifi-
cation processes. Specific outcomes of the self-modification can be
concluded as follows:
(1) The modulus, tensile stress and tensile strain of nanocellulose
modified hemp fibers increased by 36.13%, 72.80% and 67.89%,
respectively.
(2) Nanocellulose modification resulted in two different processes
on the fiber surfaces: (1) filling in the stria and (2) bonding the
inter-fibril on the surface of hemp fibers.
(3) The crystallinity of modified hemp fibers increased from
55.17% to 76.39%, showing the penetration and compatibility
of nanocellulose with microstructure layers of hemp fibers.
(4) The resin adsorption of the modified fibers increased by about
50%, indicating the change of interface properties and the ester-
ification between hydroxyl groups at C2 and C6 of nanocellulose
and carboxyl groups of unsaturated polyester.
Acknowledgement
This research programme is funded by the Technology Strategy
Board, Department for Business, Innovation and Skills, UK, Project
TP/5/SUS/6/I/H0565L.
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