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Individual cotton cellulose nanofibers: Pretreatment and fibrillation

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DOI: 10.1007/s10570-014-0172-z

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Cellulose
DOI 10.1007/s10570-014-0172-z
ORIGINAL PAPER
Individual cotton cellulose nanofibers: pretreatment
and fibrillation technique
Wenshuai Chen • Kentaro Abe • Kojiro Uetani
Haipeng Yu • Yixing Liu • Hiroyuki Yano
Received: 5 November 2013 / Accepted: 20 January 2014
Ó Springer Science+Business Media Dordrecht 2014
Abstract We report a method to fibrillate raw dried
cotton fibers into individual cellulose nanofibers
(CNFs) by chemical purification (removal of non-
cellulosic components) and pretreatment by a high-
speed blender (breaking down the fiber structures)
combined with high-pressure homogenization (nano-
fibrillation). The resultant CNFs were found to have a
width of approximately 10–30 nm and high aspect
ratios. The high light transmittance of the CNF/acrylic
resin composite indicated that our treatment success-
fully disintegrated the raw cotton fibers into uniform
CNFs. The cotton CNFs were found to have the
advantages of high crystallinity and thermal stability.
Keywords Cellulose nanofibers
Cotton

Nanofibrillation
Crystallinity
Thermal
property
Introduction
In the last decade, cellulose nanofibers (CNFs) have
received an ever increasing amount of attention
W. Chen
K. Abe
K. Uetani
H. Yano (&)
Research Institute for Sustainable Humanosphere, Kyoto
University, Uji 611-0011, Japan
e-mail: yano@rish.kyoto-u.ac.jp
W. Chen
H. Yu
Y. Liu
Key Laboratory of Bio-based Material Science and
Technology, Ministry of Education, Northeast Forestry
University, Harbin 150040, China
•
because of their remarkable structures and properties
including high aspect ratios, high crystallinity, out-
standing mechanical properties, and low coefficient of
thermal expansion (Eichhorn et al. 2010; Habibi et al.
2010; Klemm et al. 2011; Moon et al. 2011). CNFs
have been widely used in polymer nanocomposites
(Yano et al. 2005; Capadona et al. 2007; Nogi and
Yano 2008; Zhou et al. 2009; Sehaqui et al. 2011;
Kurihara and Isogai 2014), optically transparent
nanopapers (Fukuzumi et al. 2008; Nogi et al. 2009;
Hu et al. 2013; Huang et al. 2013), robust foams
(Svagan et al. 2008; Sehaqui et al. 2010) and aerogels
(Pääkkö et al. 2008; Olsson et al. 2010; Saito et al.
2011; Chen et al. 2011a), and many others. In general,
CNFs are produced as the framework of plant cell
walls in nature and have been isolated from various
natural resources such as wood (Abe et al. 2007; Abe
and Yano 2009), bamboo (Abe and Yano 2010; Chen
et al. 2011b), rice straw (Abe and Yano 2009), and
many others. The lignin and hemicelluloses contained
within the cell walls in these raw materials can be
removed by chemical treatment with NaClO2 and
KOH (alkali) solutions, respectively. After chemical
treatment, interspaces are produced between the CNFs
within the pulp (Abe et al. 2007; Chen et al. 2011b).
Mechanical treatment by a grinder (Abe et al. 2007), a
blender (Uetani and Yano, 2010), or a high-intensity
ultra-sonicator (Chen et al. 2011c) can be used to
disintegrate pulps into individual CNFs before drying.
Alkali treatments (Abe et al. 2007; Abe and Yano
2009, 2010; Chen et al. 2011b) only remove certain
123

parts of the hemicelluloses and the surfaces of the
CNFs are still covered with alkali-insoluble hemicel-
luloses (Iwamoto et al. 2008). This is a critical factor
that affects the ease of nanofibrillation. However,
hemicelluloses usually decrease the apparent crystal-
linity and thermal stability of the CNFs. Therefore,
obtaining CNFs with minimal hemicellulose surface
coverage is important for an improvement in their
physicochemical properties. Since hemicelluloses are
removed from cellulose pulp with difficulty, even
upon alkali (Iwamoto et al. 2008), acid (Chen et al.
2011b), or enzyme (Pääkkö et al. 2007) treatments, the
production of high purity CNFs remains a significant
challenge.
Cotton fibers are known to be high purity cellulose
materials and they are abundant, renewable, and
important in people’s daily lives (Wakelyn and
Bertoniere 2006). Many successful preparations of
short cotton nanowhiskers have been reported by
hydrolysis with strong acids such as HCl (Espinosa
et al. 2013), H2SO4 (Elazzouzi-Hafraoui et al. 2007)
and H3PO4 (Espinosa et al. 2013). However, reports
about the individualization of high aspect ratio CNFs
from cotton are limited. Saito et al. (2006) prepared
CNFs with a high amount of carboxylate groups on
their surface from cotton fibers using TEMPO-med-
iated oxidation combined with mechanical treatment.
Zhao et al. (2007) also successfully obtained CNFs of
30–120 nm in width from cotton fibers using an
ultrasonic method. To our knowledge, however,
reports on the isolation of uniform CNFs from cotton
without surface modification are not reported yet.
As cotton cell walls consist of high purity CNFs,
strong hydrogen bonding occurs between CNFs when
they are dried. Consequently, the extraction of long
and high purity CNFs as they exist within the cotton
cell walls is difficult when using any simple one-step
chemical or mechanical methods. In this work, we
investigated a method for the extraction of high purity
CNFs from raw cotton fibers and succeeded in
obtaining CNFs with a uniform width of 10–30 nm,
by mild chemical treatment and mechanical proces-
sion combined with a blender and a high-pressure
homogenizer. The degree of nanofibrillation was
assessed by scanning electron microscopy (SEM)
and by measuring the light transmittance of the CNF/
acrylic resin composite. The crystallinity and thermal
stability of our cotton CNFs were compared with 6
123
Cellulose
other kinds of nanocellulose that were produced using
previously reported conventional methods.
Materials and methods
Raw materials
Raw cotton fibers were purchased from Sogo Labo-
ratory Glass Works Co., LTD (TOPÒ). All chemicals
were purchased from Aldrich and Kanto Chemical,
and used as received.
Removal of non-cellulosic components
The raw cotton fibers were purified using an acidified
sodium chlorite solution at 75 °C for an hour to
remove the impurities attached to the surface of the
cotton during cotton growth and harvesting; the
process was repeated three times. The samples were
then treated overnight with 8 wt% sodium hydroxide
at room temperature followed by treatment at 80 °C
for 2 h in the same type of solution to remove all
protein, pectin, wax, sugar and organic acids. The
samples were then treated with a 1 wt% hydrochloric
acid (HCl) solution at 80 °C for 2 h to remove trace
amounts of alkali-insoluble matrixes, resulting in
purified cotton fibers.
Fibrillation of purified cotton fibers using a grinder
A *0.8 wt% suspension of purified cotton fibers was
passed once through a grinder (MKCA6-3; Masuko
Sangyo Co., Ltd., Saitama, Japan) at 1,500 rpm
containing specially adjusted grinding stones, to
produce grinder-treated cotton fibers.
Fibrillation of purified cotton fibers using a blender
A suspension of *0.3 wt% purified cotton fibers was
agitated using a high-speed blender (with an ABS-
BU motor, Vita Mix and a CAC90B X-TREME 2 L
bottle, WARING) at a stirring speed of 37,000 rpm.
An accompanying tamper (PN-D2, Vita Mix) was
used to accelerate the blending operation. After
45 min of stirring, blender-treated cotton fibers were
obtained.
Cellulose
Disintegration of purified cotton fibers using
a blender and a high-pressure homogenizer
A suspension of *0.3 wt% purified cotton fibers was
stirred in a high-speed blender for 10 min and then the
sample was roughly filtered using a metal mesh with
300-lm pores. The wet cake-like elements that
remained on the mesh were repeatedly stirred until
all the elements passed through the metal mesh and
blender-pretreated cotton fibers were obtained. A
slurry of the blender-pretreated cotton fibers in water
(0.3 wt%, 800 mL) was then passed through a high-
pressure homogenizer (Star Burst 10, HJP-25008 K,
Sugino Machine CO., Ltd., Japan) at a pressure of ca.
200 MPa at 15 °C. Unfibrillated or partially fibrillated
fibers were removed from the suspension by filtration
using a metal mesh with 50-lm pores, and they were
repeatedly subjected to homogenizer treatment until
all the fibers passed through the mesh. An aqueous
suspension of CNFs was obtained and stored at 4 °C.
Preparation of grinder-treated wood nanofibers
The method is a slight modification of the procedure
reported by Abe et al. (2007). Wood powder from
Hinoki powder (Chamaecyparis obtuse) was used as
the raw material. First, the lignin in the sample was
removed using an acidified sodium chlorite solution at
70 °C for 1 h, and the process was repeated five times.
Second, the sample was treated with 5 wt% potassium
hydroxide overnight at room temperature and then at
the same concentration at 90 °C for 2 h to remove
hemicelluloses, resulting in chemically purified wood
cellulose. The 1 wt% slurry of purified cellulose was
passed once through a grinder (MKCA6-3; Masuko
Sangyo Co., Ltd., Saitama, Japan) at 1,500 rpm,
resulting in grinder-treated wood nanofibers.
Preparation of H2SO4-hydrolyzed cotton
nanowhiskers
8 g of cotton fibers were hydrolyzed in 800 g of
55 wt% H2SO4 aqueous solution. The mixture was
occasionally stirred at 60 °C for 2 h. The suspension
was diluted and then thoroughly washed with distilled
water under filtration with a membrane filter, until the
pH of the suspension was around 4. The suspension
was finally subjected to blender treatment at a stirring
speed of 37,000 rpm for 1 min, resulting in H2SO4-
hydrolyzed cotton nanowhiskers.
Preparation of blender-treated wood nanofibers
The chemically purified wood cellulose fibers pre-
pared for grinder treatment were also used as raw
materials for blender treatment. The method is
reported in our previous paper (Uetani and Yano
2010). A suspension of 0.7 wt% chemically purified
cellulose fibers was agitated using a blender (with an
ABS-BU motor, Vita Mix and a CAC90B X-TREME
2 L bottle, WARING) at a stir speed of 37,000 rpm for
45 min, resulting in blender-treated wood nanofibers.
Preparation of TEMPO-oxidized wood nanofibers
The wood pulp (1 g) from Japanese cedar (Crypto-
meria japonica) was oxidized with TEMPO (0.02 g),
NaBr (0.15 g) and NaClO (3.2 g) in water (100 mL) at
room temperature and at a pH around 10 until no
further consumption of 0.5 M NaOH was observed,
according to the reported method (Saito et al. 2006).
After washing thoroughly with water, a 0.3 wt% slurry
of TEMPO-oxidized cellulose in water was agitated
using a high-speed blender (with an ABS-BU motor,
Vita Mix, and a CAC90B X-TREME 2 L bottle,
Waring) at a stirring speed of 37,000 rpm for 10 min,
resulting in TEMPO-oxidized wood nanofibers.
Preparation of H2SO4-hydrolyzed tunicate
nanofibers and H2SO4-hydrolyzed tunicate
nanowhiskers
The methods used for the preparation of H2SO4-
hydrolyzed tunicate nanofibers and H2SO4-hydro-
lyzed tunicate nanowhiskers were based on our
previous paper (Uetani and Yano 2013). Wet tunicate
of ascidian was used as the raw material. After
bleaching, the product was freeze-dried to obtain a
purified cellulose framework. It was then subjected to
H2SO4 hydrolysis after which the suspension was
washed with Milli-Q water until the pH was around 4.
The suspension was diluted and sonicated followed by
filtration using a metal mesh to obtain H2SO4-hydro-
lyzed tunicate nanowhiskers. A 0.13 vol % suspension
of H2SO4-hydrolyzed tunicate nanofibers was fibril-
lated from the residual cellulose after obtaining the
123

tunicate nanowhiskers, by treated with a high speed
blender at 37,000 rpm for 20 min.
CNF/resin composites
The cotton CNFs were stirred using a magnetic stirrer
for 3 h for good dispersion. The aqueous suspension
was vacuum-filtered using a polytetrafluoroethylene
membrane filter (0.1 lm mesh) to form a wet mat. The
wet mat was then immersed in ethanol overnight to
exchange the solvent followed by hot-pressing at
110 °C with 3 kg/cm2 for 15 min. The sheet was then
immersed in acrylic resin (ABPE-10, Shin-Nakamura
Chemical Co. Ltd, refractive index: 1.516) and was
kept under reduced pressure for 2 h. The composite
was then cured by UV light. The thickness of the
composite was determined as an average of five
measurements using a micrometer.
Characterization
Transmission electron microscopy (TEM) images were
obtained using a JEM-200 (JEOL Co. Ltd) operating at
100 kV. The samples were negatively stained with
2 wt% uranyl acetate to enhance the microscopic
resolution. Field emission scanning electron micros-
copy (FE-SEM) images were captured using a JSM-
6700F (JEOL) with a Pt coating (*2 nm) that was
applied using an ion sputter coater (JFC-1600, JEOL).
The widths of the CNFs were measured using a
microscopy image analysis system (TDY-V5.2, Beijing
Tianhong Precision Instrument Technology Co., Ltd.),
and this was used to determine the size distributions. The
micro-sized fibers, dispersed in water, were directly
observed using an optical microscope (VHX-200,
Keyence). The light transmittance of the composites
was measured using a UV–visible spectrometer at
wavelengths from 300 to 800 nm with an integrating
sphere 60 mm in diameter (U-4100, Hitachi High Tech.
Corp.). The suspension viscosity was determined using
a rotary viscometer (Visco Basic Plus, Fungilab S.A).
The test temperature for all the samples was controlled
at 20 °C. X-ray diffraction profiles were obtained with
Ni-filtered CuKa (k = 0.154 nm) radiation using an
X-ray generator (UltraX 18HF, Rigaku Corp.) operating
at 40 kV and 30 mA. Scattered radiation was detected at
2h = 5–40°. The crystallinity index was calculated
according to the Segal method (Segal et al. 1959).
Thermogravimetric (TG) analysis was performed on a
123
Cellulose
Q-50 (TA Instruments) under a nitrogen atmosphere
(60 mL/min) at a heating rate of 10 °C/min. The a-
cellulose content of the samples was determined by
extraction with 17.5 wt% NaOH according to a method
reported previously (Chen et al. 2011d).
Results and discussion
Removal of non-cellulosic components
Dried raw cotton was used as a starting material. Non-
cellulosic components such as pectins and proteina-
ceous materials are known to be located mainly in the
outer waxy layer (cuticle layer) (Wakelyn and Bertoni-
ere 2006). These components serve as a smooth, water-
resistant protective coating, which is thought to inter-
rupt nanofibrillation. Thus, a series of chemical treat-
ments was performed to purify the cotton fiber surfaces.
Figures 1 and 2 show images of raw cotton and the
chemically purified fibers. The raw cotton fibers have
twisted ribbon-like structures. Since non-cellulosic
components cover the fiber surface, single CNFs are
difficult to observe (Fig. 2a). NaClO2 treatment under
acidic conditions was thus employed to remove the
impurities attached to the surfaces of the fibers. The
twisted ribbon-like structure of the cotton fibers was
observed to show little change after NaClO2 treatment.
However, CNF characteristics were occasionally
observed for the treated fibers (Fig. 2b). Subsequently,
these cotton fibers were further treated using an 8 wt%
NaOH aqueous solution to remove wax, protein, pectin,
ash, and organic acids (Wakelyn and Bertoniere 2006).
The fibers became untwisted and flat. The CNFs could
now be clearly observed on both sides of the flat cotton
fibers (Fig. 2c). However, non-cellulosic polymers or
other components were still present on the fiber surface
to some extent. The fibers were then treated with a
1 wt% HCl aqueous solution to remove trace amounts
of alkali-insoluble components. We also expected that
HCl treatment may partially decrease the hydrogen
bonding force between adjacent CNFs. After HCl
treatment, we confirmed the high purity of cellulose of
cotton fibers (a-cellulose content of *100 %). The
HCl-treated fibers were flat and the CNFs were clearly
observed from the fiber surfaces (Fig. 2d).
Figure 2e shows the XRD profiles of raw cotton and
the chemically purified fibers. All the samples have
diffraction peaks at 14.6°, 16.5°, and 22.6°, which
Cellulose

Fig. 1 Optical microscope

images of (a, b) raw cotton
fibers and chemically
purified cotton fibers after
NaClO2 treatment (c, d),
8 wt% NaOH treatment (e,
f), and 1 wt% HCl treatment
(g, h). The scale bar for (a,
c, e, g) is 500 lm (left
panel), while the scale bar
for (b, d, f, h) is 50 lm
(right panel)

correspond to the (1–10), (110), and (200) diffraction
planes, respectively. These are typical crystalline
patterns of the cellulose I type, indicating that the
native cellulose I crystalline structure remained intact
during the chemical purification. The relative crystal-
linity increased from 82.3 % for the raw cotton fibers
to around 85.7 % for the NaOH-treated fibers because
of the removal of non-cellulosic components. The
crystallinity of the HCl-treated fibers (84.9 %) was
similar to that of the NaOH-treated fibers. The thermal
stability of the fibers was found to gradually decrease
as the chemical treatments progressed (Fig. 2f).

123
 Cellulose

Fig. 2 FE-SEM images of

(a) raw cotton fibers and
chemically purified cotton
fibers after NaClO2
treatment (b), 8 wt% NaOH
treatment (c), and 1 wt%
HCl treatment (d). e X-ray
diffraction patterns and f TG
curves of the raw cotton
fibers and the chemically
purified cotton fibers. The
scale bar of 200 nm applies
to all images

Compared with the NaOH-treated fibers, the deriva-
tive thermogravimetric peak of the HCl-treated fibers
decreased obviously.
Fibrillation of purified cotton fibers using a grinder
and a blender
The 0.8 wt% aqueous suspension of purified cotton
fibers was treated once using a grinder. Although the
grinder is able to produce nanofibers from wood (Abe
et al. 2007) or chitin shells (Ifuku et al. 2009) with a fine
structure of 10–20 nm in width in just one pass, the
cotton fibers after one pass through the grinder had non-
uniform structures (Fig. 3a). Because of remaining the
strong hydrogen bonding between the adjacent cotton
CNFs after the chemical purification, tightly connected
CNFs were still present during grinder treatment. The
suspension had a low viscosity and aggregates were
easily formed. Large particles precipitated and were
found at the bottom of the bottle after setting up for 5 h.
The grinder treatment was, therefore, unable to fibrillate
the cotton fibers into CNFs with a uniform width.
A high-speed blender, which allows for the disin-
tegration of the S1 layer of wood pulp and thus
nanofibrillation (Uetani and Yano 2010) was used to
fibrillate the chemically purified cotton fibers at
37,000 rpm for 45 min. Figure 3b shows a FE-SEM
image of the blender-treated cotton fibers. Although
the cell wall structure was broken, the blender-treated
fibers remained as lamella structures, and these are

123
Cellulose
Fig. 3 FE-SEM images of the cotton fibers after fibrillation
using a a grinder and b a blender. The scale bar of 1 lm applies
to all images
often observed within cotton cell walls (Wakelyn and
Bertoniere 2006). The width of the lamella ranged
from several to several tens of microns. The lamella
bundles were organized as long and aligned CNFs.
Production of cotton CNFs using a combination
of a blender and a high-pressure homogenizer
treatment
High-pressure homogenization is a well-known effi-
cient method to produce CNFs (Herrick et al. 1983;
Turbak et al. 1983). The cellulosic fiber suspension was
pumped under high pressure through a spring-loaded
valve assembly. The valve opens and closes by a
reciprocating motion and the micro-sized fibers are
subjected to shear and impact forces upon the large
pressure drop and they disintegrate into individual
CNFs (Nakagaito and Yano 2005). Our purified cotton
fibers, however, were still large and easily blocked the
flow channels inside the homogenizer, and thus the fiber
Fig. 4 FE-SEM images of the cotton fibers after nanofibrilla-
tion with a high pressure homogenizer for a 30 min and
b 50 min. The scale bar of 1 lm applies to all images
sizes needed to be reduced before passing. Considering
that a blender fragments the fibers into smaller fractions
(Uetani and Yano 2010) and also preserves the length of
the CNFs (Uetani and Yano 2013), high-speed blender
treatment was performed as a pretreatment for the large
cotton fibers before passing through the homogenizer.
The samples after blender treatment were passed
through a metal mesh with 300 lm pores, resulting in
the lamella bundles consist of highly aligned CNFs of
several hundred microns in length. The blender-
pretreated fiber suspension of around 800 ml at a
concentration of 0.3 wt% was then subjected to a high-
pressure homogenizer followed by passing through a
50 lm metal mesh to remove the long and large
bundles. Figure 4a and b shows FE-SEM images of the
CNFs after treatment through a high-pressure homog-
enizer for 30 and 50 min, respectively. Although long
and single CNFs can be clearly observed, many large
bundles were still present. When increasing the
homogenizer treatment time to 2 h, a uniform and
123

Fig. 5 a TEM image of
cotton CNFs. The inset in
(a) shows the cotton CNF
suspension with the
concentration of
*0.03 wt%. b, c FE-SEM
images of the cotton CNFs
stable suspension was finally obtained (See inset in
Fig. 5a). Observation by TEM (Fig. 5a) indicated that
the suspension consisted of long bundles with parallel-
aligned nanofibrils of 6–12 nm in width. Small amounts
of short nanofibrils were also present. After oven
drying, the nanofibrils within the bundles self-aggre-
gated along the longitudinal direction and high aspect
ratio CNFs were formed (Fig. 5b). The individual
CNFs had a highly uniform width of approximately
10–30 nm, as shown by the extensive area (Fig. 5c).
CNF/acrylic resin composites of *120 lm in thick-
ness were produced to evaluate the degree of nanofi-
brillation of the cotton fibers (See Fig. 6a). The CNF
content of the composite was measured as *33 wt%.
The composite showed high flexibility and transparency
(Fig. 6). The linear and total transmittances were a
respective 76.4 and 84.7 % at a 600 nm wavelength.
Characterization of cotton CNFs
The viscosity, crystallinity and thermal stability of our
cotton CNFs were compared with grinder-treated
wood nanofibers and H2SO4-hydrolyzed cotton nano-
whiskers. For clarity, the cotton CNFs are referred to
123
Cellulose
as cotton nanofibers in this section. A schematic model
and FE-SEM images of the three kinds of nanocellu-
lose are shown in Fig. 7a and c–e, respectively. The
viscosity of the nanocellulose suspensions increased
proportionally to the concentrations (Fig. 7b). The
wood nanofiber suspension exhibited the highest
viscosities of 68.5–329.6 mPa s in a concentration
range from 0.25 to 0.5 wt%, respectively. Because
little hemicelluloses cover the nanofiber surfaces, the
viscosities of the cotton nanofiber suspension was
lower than that of wood nanofibers, which ranged from
84.6 mPa s to 302.5 mPa s with an increase in
concentration from 0.4 to 0.65 wt%. On the other
hand, suspensions of the cotton nanowhiskers gave
ultra-low viscosities because of their low aspect ratios.
Even at a nanowhisker concentration of 3.2 wt%, the
viscosity was still as low as 142.5 mPa s.
The native cellulose I type crystalline structure was
confirmed for each kind of nanocellulose (Fig. 8a).
The relative crystallinity of 88.8 % for the cotton
nanofibers was higher than that for wood nanofibers at
75.3 %. Although the cotton nanowhiskers showed the
highest crystallinity of 93.1 %, their thermal stability
was much lower than that of the cotton and wood
Cellulose
Fig. 6 Linear and total light transmittance spectra of the cotton
CNF/acrylic resin composite. The inset shows the appearance of
the composite
Fig. 7 a A schematic model of cotton nanofibers (left),
grinder-treated wood nanofibers (middle), and H2SO4-hydro-
lyzed cotton nanowhiskers (right). b The viscosity of the three
kinds of nanocellulose suspensions. FE-SEM images of c cotton
nanofibers (Fig. 8b). The reason is that the sulfate
groups on the cotton nanowhisker surfaces promote
rapid thermal degradation (Roman and Winter 2004).
The cotton nanofibers had a higher thermal degrada-
tion temperature of 325.4 °C than that of the wood
nanofibers, which was 286.7 °C. The high thermal
performance of the cotton nanofibers is mainly
attributed to their high cellulose content. Cotton
nanofibers are nearly 100 % cellulose without hemi-
celluloses covered on the surfaces, but wood nanof-
ibers contain 80–85 % cellulose with 15–20 %
hemicelluloses and little amounts of other impurities
covered on the surfaces (Iwamoto et al. 2008; Chen
et al. 2011d). The pyrolysis of hemicelluloses starts
earlier than cellulose. The weight loss of hemicellu-
loses mainly happened at 220–315 °C and that of
cellulose at 315–400 °C (Yang et al. 2007). Thus, the
nanofibers, d grinder-treated wood nanofibers, and e H2SO4-
hydrolyzed cotton nanowhiskers. The scale bar of 200 nm
applies to all images
123

Fig. 8 a X-ray diffraction patterns and b TG curves of cotton
nanofibers, grinder-treated wood nanofibers, and H2SO4-hydro-
lyzed cotton nanowhiskers. c Comparison of the thermal
cotton nanofibers exhibit higher thermal stability than
wood nanofibers.
Because nanocellulose with different structures and
properties can be extracted from different resources
using variety nanofibrillation methods, the advantage
of cotton nanofibers was investigated by further
comparing their crystallinity and thermal degradation
temperature to those of blender-treated wood nanof-
ibers, TEMPO-oxidized wood nanofibers, H2SO4-
hydrolyzed tunicate nanofibers and H2SO4-hydro-
lyzed tunicate nanowhiskers. The chart in Fig. 8c
reveals that our cotton nanofibers have advantages of
high crystallinity and a high thermal property with
relatively high aspect ratios.
Conclusion
In summary, raw cotton fibers were disintegrated by
considering the order of removing the components and
the mechanical fibrillation combined with a blender
and a high-pressure homogenizer. The cotton CNFs
had a width of approximately 10–30 nm. The viscos-
ities of the CNF suspensions ranged from 84.6 to
302.5 mPa s, with an increase in concentration from
0.4 to 0.65 wt%, respectively. Because of their high
purity with small amounts of amorphous polymers
(such as hemicelluloses or other impurities), the cotton
CNFs had higher crystallinity and thermal stability
compared with six other kinds of nanocellulose.
Cotton CNFs are promising nanofibers for a wide
range of applications and can replace existing CNFs
because of their renewability, abundance, high purity,
high aspect ratio, high crystallinity, and high thermal
123
Cellulose
degradation temperature and crystallinity of cotton nanofibers
with the values for six other kinds of nanocellulose
stability. Cotton CNFs can also contribute to the
determination of the effects or properties of hemicel-
luloses within materials.
Acknowledgments We thank Dr Thi Thu Thao Ho, of the
Research Institute for Sustainable Humanosphere, Kyoto
University, for her kind help in using a high-pressure
homogenizer, and for fruitful discussions on the data analysis.
We are also grateful to thank Dr Yoshiki Horikawa, of the
Research Institute for Sustainable Humanosphere, Kyoto
University, for the staining of the TEM samples. Wenshuai
Chen was also partially supported by the Program for New
Century Excellent Talents in University (NCET-10-0313),
China.
References
Abe K, Iwamoto S, Yano H (2007) Obtaining cellulose nanof-
ibers with a uniform width of 15 nm from wood. Bio-
macromol 8(10):3276–3278
Abe K, Yano H (2009) Comparison of the characteristics of
cellulose microfibril aggregates of wood, rice straw and
potato tuber. Cellulose 16(6):1017–1023
Abe K, Yano H (2010) Comparison of the characteristics of
cellulose microfibril aggregates isolated from fiber and
parenchyma cells of Moso bamboo (Phyllostachys pubes-
cens). Cellulose 17(2):271–277
Capadona JR, Van Den Berg O, Capadona LA, Schroeter M,
Rowan SJ, Tyler DJ, Weder C (2007) A versatile approach
for the processing of polymer nanocomposites with self-
assembled nanofibre templates. Nat Nanotechnol 2(12):
765–769
Chen W, Yu H, Li Q, Liu Y, Li J (2011a) Ultralight and highly
flexible aerogels with long cellulose I nanofibers. Soft
Matter 7(21):10360–10368
Chen W, Yu H, Liu Y (2011b) Preparation of millimeter-long
cellulose I nanofibers with diameters of 30–80 nm from
bamboo fibers. Carbohydr Polym 86(2):453–461
Chen W, Yu H, Liu Y, Chen P, Zhang M, Ha Y (2011c) Indi-
vidualization of cellulose nanofibers from wood using
Cellulose
high-intensity ultrasonication combined with chemical
pretreatments. Carbohydr Polym 83(4):1804–1811
Chen W, Yu H, Liu Y, Hai Y, Zhang M, Chen P (2011d) Iso-
lation and characterization of cellulose nanofibers from
four plant cellulose fibers using a chemical-ultrasonic
process. Cellulose 18(2):433–442
Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Ca-
padona JR, Rowan SJ, Weder C, Thielemans W, Roman M,
Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K,
Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight
AS, Bismarck A, Berglund LA, Peijs T (2010) Review:
current international research into cellulose nanofibres and
nanocomposites. J Mater Sci 45(1):1–33
Elazzouzi-Hafraoui S, Nishiyama Y, Putaux JL, Heux L, Dub-
reuil F, Rochas C (2007) The shape and size distribution of
crystalline nanoparticles prepared by acid hydrolysis of
native cellulose. Biomacromol 9(1):57–65
Espinosa SC, Kuhnt T, Foster EJ, Weder C (2013) Isolation of
thermally stable cellulose nanocrystals by phosphoric acid
hydrolysis. Biomacromol 14:1223–1230
Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2008)
Transparent and high gas barrier films of cellulose nanof-
ibers prepared by TEMPO-mediated oxidation. Biomac-
romol 10(1):162–165
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals:
chemistry, self-assembly, and applications. Chem Rev
110(6):3479–3500
Herrick FW, Casebier RL, Hamilton JK (1983) Microfibrillated
cellulose: morphology and accessibility. J Appl Polym Sci
Appl Polym Symp 37:797–813
Hu L, Zheng G, Yao J, Liu N, Weil B, Eskilsson M, Karabulut E,
Ruan Z, Fan S, Bloking JT, McGehee MD, Wågberg L, Cui
Y (2013) Transparent and conductive paper from nano-
cellulose fibers. Energ Environ Sci 6(2):513–518
Huang J, Zhu H, Chen Y, Preston C, Rohrbach K, Cumings J, Hu
L (2013) Highly transparent and flexible nanopaper tran-
sistors. ACS Nano 7(3):2106–2113
Ifuku S, Nogi M, Abe K, Yoshioka M, Morimoto M, Saimoto H,
Yano H (2009) Preparation of chitin nanofibers with a
uniform width as a-chitin from crab shells. Biomacromol
10(6):1584–1588
Iwamoto S, Abe K, Yano H (2008) The effect of hemicelluloses
on wood pulp nanofibrillation and nanofiber network
characteristics. Biomacromol 9(3):1022–1026
Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray
D, Dorris A (2011) Nanocelluloses: a new family of nature-
based materials. Angew Chem Int Edit 50(24):5438–5466
Kurihara T, Isogai A (2014) Properties of poly (acrylamide)/
TEMPO-oxidized cellulose nanofibril composite films.
Cellulose. doi:10.1007/s10570-013-0124-z
Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011)
Cellulose nanomaterials review: structure, properties and
nanocomposites. Chem Soc Rev 40(7):3941–3994
Nakagaito A, Yano H (2005) Novel high-strength biocomposites
based on microfibrillated cellulose having nano-order-unit
web-like network structure. Appl Phys A 80(1):155–159
Nogi M, Yano H (2008) Transparent nanocomposites based on
cellulose produced by bacteria offer potential innovation in
the electronics device industry. Adv Mater 20(10):1849–
1852
Nogi M, Iwamoto S, Nakagaito AN, Yano H (2009) Optically
transparent nanofiber paper. Adv Mater 21(16):1595–1598
Olsson RT, Azizi Samir MAS, Salazar-Alvarez G, Belova L,
Ström V, Berglund LA, Ikkala O, Nogues J, Gedde UW
(2010) Making flexible magnetic aerogels and stiff mag-
netic nanopaper using cellulose nanofibrils as templates.
Nat Nanotechnol 5(8):584–588
Pääkkö M, Ankerfors M, Kosonen H, Nykänen A, Ahola S,
Österberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala
O, Lindström T (2007) Enzymatic hydrolysis combined
with mechanical shearing and high-pressure homogeniza-
tion for nanoscale cellulose fibrils and strong gels. Bio-
macromol 8(6):1934–1941
Pääkkö M, Vapaavuori J, Silvennoinen R, Kosonen H, An-
kerfors M, Lindström T, Berglund LA, Ikkala O (2008)
Long and entangled native cellulose I nanofibers allow
flexible aerogels and hierarchically porous templates for
functionalities. Soft Matter 4(12):2492–2499
Roman M, Winter WT (2004) Effect of sulfate groups from
sulfuric acid hydrolysis on the thermal degradation
behavior of bacterial cellulose. Biomacromol 5:1671–1677
Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006)
Homogeneous suspensions of individualized microfibrils
from TEMPO-catalyzed oxidation of native cellulose.
Biomacromol 7(6):1687–1691
Saito T, Uematsu T, Kimura S, Enomae T, Isogai A (2011) Self-
aligned integration of native cellulose nanofibrils towards
producing diverse bulk materials. Soft Matter 7(19):8804–
8809
Segal L, Creely J, Martin A, Conrad C (1959) An empirical
method for estimating the degree of crystallinity of native
cellulose using the X-ray diffractometer. Text Res J
29(10):786–794
Sehaqui H, Salajková M, Zhou Q, Berglund LA (2010)
Mechanical performance tailoring of tough ultra-high
porosity foams prepared from cellulose I nanofiber sus-
pensions. Soft Matter 6(8):1824–1832
Sehaqui H, Zhou Q, Berglund LA (2011) Nanostructured bio-
composites of high toughness—a wood cellulose nanofiber
network in ductile hydroxyethylcellulose matrix. Soft
Matter 7(16):7342–7350
Svagan AJ, Samir MASA, Berglund LA (2008) Biomimetic
foams of high mechanical performance based on nano-
structured cell walls reinforced by native cellulose nano-
fibrils. Adv Mater 20(7):1263–1269
Turbak AF, Snyder FW, Sandberg KR (1983) Microfibrillated
cellulose, a new cellulose product: properties, uses, and
commercial potential. J Appl Polym Sci: Appl Polym
Symp 37:815–827
Uetani K, Yano H (2010) Nanofibrillation of wood pulp using a
high-speed blender. Biomacromol 12(2):348–353
Uetani K, Yano H (2013) Self-organizing capacity of nanocel-
luloses via droplet evaporation. Soft Matter 9:3396–3401
Wakelyn PJ, Bertoniere NR (2006) Cotton Fiber Chemistry and
Technology. CRC Press
Yang H, Yan R, Chen H, Lee DH, Zheng C (2007) Character-
istics of hemicellulose, cellulose and lignin pyrolysis. Fuel
86(12):1781–1788
Yano H, Sugiyama J, Nakagaito AN, Nogi M, Matsuura
T, Hikita M, Handa K (2005) Optically transparent
123
 Cellulose

composites reinforced with networks of bacterial nanofi-
bers. Adv Mater 17(2):153–155
Zhao HP, Feng XQ, Gao H (2007) Ultrasonic technique for
extracting nanofibers from nature materials. Appl Phys Lett
90 (7): 073112-073112-2
Zhou Q, Malm E, Nilsson H, Larsson PT, Iversen T, Berglund
LA, Bulone V (2009) Nanostructured biocomposites based
on bacterial cellulosic nanofibers compartmentalized by a
soft hydroxyethylcellulose matrix coating. Soft Matter
5(21):4124–4130

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